molecules

Article
Hierarchical Porous Activated Carbon Derived from Coconut
Shell for Ultrahigh-Performance Supercapacitors
Yawei Wang 1, * , Yuhui Duan 2 , Xia Liang 1 , Liang Tang 1 , Lei Sun 1 , Ruirui Wang 1 , Shunhang Wei 3 ,
Huanan Huang 1 , Pinghua Yang 1 and Huanan Hu 1, *

1 School of Chemistry and Chemical Engineering, Jiangxi Province Engineering Research Center of Ecological
Chemical Industry, Jiujiang University, Jiujiang 332005, China; [email protected] (X.L.);
[email protected] (L.T.); [email protected] (L.S.); [email protected] (R.W.);
[email protected] (H.H.); [email protected] (P.Y.)
2 Institute for Advanced Interdisciplinary Research (iAIR), University of Jinan, Jinan 250022, China;
[email protected]
3 School of Mathematical Information, Shaoxing University, Shaoxing 312000, China; [email protected]
* Correspondence: [email protected] (Y.W.); [email protected] (H.H.)

Abstract: In this research, we successfully produced hierarchical porous activated carbon from
biowaste employing one-step KOH activation and applied as ultrahigh-performance supercapacitor
electrode materials. The coconut shell-derived activated carbon (CSAC) features a hierarchical porous
structure in a honeycomb-like morphology, leading to a high specific surface area (2228 m2 g−1 ) as
well as a significant pore volume (1.07 cm3 g−1 ). The initial test with the CSAC electrode, conducted
in a 6 M KOH loaded symmetric supercapacitor, demonstrated an ultrahigh capacitance of 367 F g−1
at a current density of 0.2 A g−1 together with 92.09% retention after 10,000 cycles at 10 A g−1 .
More impressively, the zinc–ion hybrid supercapacitor using CSAC as a cathode achieves a high-
rate capability (153 mAh g−1 at 0.2 A g−1 and 75 mAh g−1 at 10 A g−1 ), high energy density
(134.9 Wh kg−1 at 175 W kg−1 ), as well as exceptional cycling stability (93.81% capacity retention
after 10,000 cycles at 10 A g−1 ). Such work thus illuminates a new pathway for converting biowaste-
Citation: Wang, Y.; Duan, Y.; Liang, derived carbons into materials for ultrahigh-performance energy storge applications.
X.; Tang, L.; Sun, L.; Wang, R.; Wei, S.;
Huang, H.; Yang, P.; Hu, H.
Keywords: hierarchical porous activated carbon; coconut shells; ultrahigh-performance; KOH
Hierarchical Porous Activated
symmetric supercapacitors; zinc–ion hybrid supercapacitors
Carbon Derived from Coconut Shell
for Ultrahigh-Performance
Supercapacitors. Molecules 2023, 28,
7187. https://doi.org/10.3390/
molecules28207187
1. Introduction
In order to address the escalating demand for energy, continuous advancements have
Academic Editors: Yuanyuan Zhu
been achieved in the domain of energy conversion and storage devices [1,2]. Supercapaci-
and Yanmin Jia
tors, which may fill the gap between traditional capacitors and rechargeable batteries in
Received: 9 September 2023 terms of energy storage, have intrigued researchers much because of their high power
Revised: 9 October 2023 density, excellent cycling stability, and swift charge–discharge speed [3–5]. Nevertheless, to
Accepted: 18 October 2023 meet the long endurance requirements of actual applications, supercapacitors are deemed
Published: 20 October 2023 to be designed with a high energy density. The voltage window (V) and the capacitance
(C) of the supercapacitor can be elevated to increase the energy density (E) in accordance
with the formula E = 1/2CV 2 [6]. Generally, the working voltage depends on the stable
electrochemical window of the electrolyte, whereas the capacitance is dictated by the physic-
Copyright: © 2023 by the authors.
ochemical properties of electrode materials [7,8]. As a result, multiple supercapacitors are
Licensee MDPI, Basel, Switzerland.
This article is an open access article
proposed to hasten the energy/power density ratio by creating new electrode/electrolyte
distributed under the terms and
materials and optimizing the design of supercapacitors [9,10].
conditions of the Creative Commons Due to their high surface area and suitable porous structure, which are the primary
Attribution (CC BY) license (https:// factors affecting electrochemical energy storage in supercapacitors, hierarchical porous
creativecommons.org/licenses/by/ activated carbons (HPACs) have been acknowledged as active electrode materials in vary-
4.0/). ing supercapacitors [11,12]. Electrolyte ions move swiftly from the macropores to the

Molecules 2023, 28, 7187. https://doi.org/10.3390/molecules28207187 https://www.mdpi.com/journal/molecules

Molecules 2023, 28, 7187 2 of 14

micropores through the mesoporous pathways in hierarchical porous structures, achieving

the necessary adsorption of ions on the substantial specific surface area [13,14]. Thereby,
developing HPACs with a large surface area has been considered an appealing choice for
enhancing supercapacitors’ ability to store energy [15]. Typically, HPACs are produced
from fossil feedstocks or organic polymers using template or physicochemical activation
methods [16–19]. However, the consumption of organic polymers, fossil fuels and tem-
plates unavoidably increases the price of HPACs synthesis, further hindering their broad
use in supercapacitors. Biowaste materials, including pitaya peel [20], corncob [21], bio-
oil [22], durian kernel [23] and sesame husk [24], have been employed to create HPACs
on an industrial large-scale and also served as electrode materials in supercapacitors due
to their unignorable benefit of low cost [25]. Among various biowaste-based superca-
pacitors, zinc–ion hybrid supercapacitors (ZHSs) directly utilize naturally abundant zinc
foils as the anode, biowaste-derived carbons as the cathode materials and neutral elec-
trolytes (ZnSO4 or Zn(CF3 SO3 )2 ) for a comparatively high working voltage (~1.8 V in the
aqueous electrolyte) [26,27]. Therefore, such a ZHSs system, which inherits the merits of
high-power supercapacitors and high-energy batteries, have gained extensive interest due
to their superior energy/power ratio, dependable safety, low cost and high theoretical
capacity (~820 mAh g−1 ) [28,29]. Leveraging the distinctive design of HPACs, derived from
biowaste, as cathode materials can effectively meet the high energy storage performance
and industrial-production demands of ZHSs in today’s market. For instance, Zhang et al.
applied pencil-shaving derived porous carbon as a cathode material and the assembled
ZHSs obtained a superior capacity of 183 mAh g−1 at 0.2 A g−1 in Zn(CF3 SO3 )2 electrolyte
with 92.2% capacity retention after 10,000 cycles [30]. Chen et al. prepared N, O co-doped
2D carbon nanosheets from poplar wood and achieved a capacity of 111.0 mAh g−1 at
0.1 A g−1 in 2 M ZnSO4 electrolyte [31].
Herein, due to the enormous annual production of coconuts (~60 million tons world-
wide), coconut shell was chosen in this study as the possible precursor for the large-scale
manufacturing of HPAC and commercial application in energy storage devices. The coconut
shell-derived carbon activated by KOH (CSAC) we have prepared features a honeycomb-
like morphology, a large specific surface area and hierarchical porous structure. These
attributes equip the CSAC with a high energy storage performance and enduring cycla-
bility, performing well in both conventional symmetric and hybrid supercapacitors. Our
findings underscore the potential of HPAC derived from the coconut shell as an exceptional
electrode material for ultrahigh-performance supercapacitors.

2. Results and Discussion

The thermogravimetric curve of the precursor in Figure 1a was procured under a
nitrogen atmosphere to examine the carbonization of coconut shell. The TG curve appears
to be roughly divided into three regions: the release of absorbed water causes the mass
curve of a coconut shell to drop by around 1.35% in the purple low-temperature region
(30–150 ◦ C). The rapid heating rate of 5 ◦ C min−1 makes it that the absorbed water in the
coconut shell is difficult to be thoroughly released before 100 ◦ C in time. A cliff-like mass
decrease of 75.82% is ascribed to the elimination of pyrolysis products via the disintegration
of bio-mass molecules at the green middle-temperature range of 150–600 ◦ C. Further
carbonization causes the TG curve to steadily diminish and reach a plateau at the last
bule high-temperature area between 600 and 900 ◦ C, leaving 15.75% of the original mass.
Figure 1b shows the XRD patterns and illustrates the phase formation of all samples. The
absence of prominent potassium compound signals suggests that the carbon samples were
successfully rinsed with diluted HCl and deionized water to bring them to neutrality.
At around 23◦ and 43◦ , there are two large diffraction peaks that are attributed to the
(002) and (100) planes of amorphous carbon. The near graphitization degree is certified
by the lack of substantial difference between the diffraction peaks of CSAC and CSC.
Four Gaussian–Lorentzian peaks are fitted in Raman spectra (Figure 1c) to better compare
the graphitization degree: I band observed at 1220 cm−1 is ascribed to the impurities
Molecules 2023, 28, x FOR PEER REVIEW 3 of 14
Molecules 2023, 28, 7187 3 of 14

graphitization degree: I band observed at 1220 cm−1 is ascribed to the impurities near car-
bon atoms,
near carbonDatoms,
band around
D band1355 cm−11355
around cm−1 is attributed
is attributed to the breathing
to themode of sp2mode
breathing of sp2 -
-hybridezed
structure units
hybridezed which units
structure is active in the
which presence
is active of defects,
in the presence Dʹofband
defects, 0
positioned
D bandaround 1490
positioned
cm−1 is caused
around 1490 cm by−1the defects from
is caused by thestacked
defectsgraphene layersgraphene
from stacked and G band,layerslocated
and Gatband,
1590
located at 1590 cm−
cm−1, is connected to1 ,the vibration of
is connected to graphitic sp2-type
the vibration of graphitic sp2 -type
carbon [32,33]. Acarbon
higher [32,33].
degree of A
graphitization
higher caused
degree of by KOH activation
graphitization caused by is KOH
indicated by a lower
activation ID/IG value
is indicated by(1.50) obtained
a lower ID /IG
from CSAC,
value as assessed
(1.50) obtained fromby comparing the peak by
CSAC, as assessed area ratio of D the
comparing band andarea
peak G band
ratio(IDof/IGD
).
band and G the
In addition, bandCSC (IDand
/IG ).CSACIn addition,
both have thetheCSC and CSAC
obvious 2D bands both have the
around 2700obvious
cm , indi-
−1 2D
bands
cating around 2700 cm
the existence of − 1 , indicating the existence of layer graphene. The amorphous-like
layer graphene. The amorphous-like structure of the activated car-
structure
bon derivedof the activated
from coconut carbon
shell derived
is shownfrom coconut
by the shell
results is shown
of the by the results
XRD pattern of the
and Raman
XRD pattern
spectra and Raman
discussed above. spectra discussed above.

Figure 1.
Figure 1. (a)
(a)TG
TGcurve
curveofofcoconut
coconutshell
shellunder
underN2Natmosphere from room temperature to 900 °C, ◦(b)
2 atmosphere from room temperature to 900 C,
XRD patterns and (c) Raman spectra of CSC and CSAC.
(b) XRD patterns and (c) Raman spectra of CSC and CSAC.

The SEM and TEM images in Figure 2 show show thethe micro-morphologies
micro-morphologies and general
pore structure of CSC and CSAC. As depicted in Figure 2a, CSC has a surface covered in
rough fragments or folds, and its coarse fibers have a diameter of 160 µm (Figure 2b). The
microscopewas
optical microscope wasalso
alsoused
usedtoto inspect
inspect thethe coconut
coconut shell
shell to illustrate
to illustrate howhow fibrous
fibrous it wasit
was prior
prior to a high-temperature
to a high-temperature treatmenttreatment
(Figure(Figure S1). 2c
S1). Figure Figure
for the2c CSAC
for thesample
CSACshows sample a
shows a honeycomb-like
honeycomb-like feature
feature with with
a clear a clearstructure
porosity porosity following
structure following
a one-stepaKOH one-step KOH
activation
at 800 ◦ C for
activation at 2800
h. °C
In Figure
for 2 h.2d,In the linked
Figure 2d,pores that the
the linked CSAC
pores thatpossesses
the CSAC (depicted
possesses by(de-
red
dotted circles)
picted by with an
red dotted average
circles) withdiameter
an average of ~2.5 µm are
diameter visible
of ~2.5 µmwhen closerwhen
are visible inspection
closer
is performed.
inspection The distinctive
is performed. The porosity
distinctivearchitecture and the size and
porosity architecture of diameter
the sizewere further
of diameter
evidenced
were further by evidenced
the TEM image by the (Figure 2e). The
TEM image high-resolution
(Figure TEM image (Figure
2e). The high-resolution TEM2f) also
image
showed thealso
(Figure 2f) presence
showed ofthe
thepresence
micro- and mesopores
of the micro- and as mesopores
a disorder as structure.
a disorder There is no
structure.
obvious
There is lattice fringelattice
no obvious in thefringe
magnified
in theSAED (inset SAED
magnified of Figure 2f), of
(inset further
Figure substantiating
2f), further sub- the
amorphous state of CSAC. In addition, the unclear concentric rings in
stantiating the amorphous state of CSAC. In addition, the unclear concentric rings in the the SAED pattern are
estimated with the radius of ~4.76 and 2.94 1/nm, which are connected
SAED pattern are estimated with the radius of ~4.76 and 2.94 1/nm, which are connected to the (100) and (002)
planes, respectively.
to the (100) and (002)Herein,
planes, KOH activation
respectively. proves
Herein, KOH effective in inducing
activation a honeycomb-
proves effective in in-
like morphology
ducing with interconnected
a honeycomb-like morphologymacropores in coconutmacropores
with interconnected shell-derived in carbon
coconut[23,34].
shell-
This network
derived carbon of [23,34].
interconnected macropores
This network serves to facilitate
of interconnected macroporeselectrolyte
servesions into the
to facilitate
mesopores/micropores, thereby expediting their access to the carbon
electrolyte ions into the mesopores/micropores, thereby expediting their access to the car- materials surfaces.
This mechanism
bon materials resultsThis
surfaces. in the highly efficient
mechanism resultsuse of highly
in the the substantial
efficient usespecific
of thesurface area,
substantial
leading to an enhancement in the rate performance.
specific surface area, leading to an enhancement in the rate performance.
Molecules 2023, 28, x7187
FOR PEER REVIEW 4 4of
of 14
14

SEM images of (a,b) CSC and

Figure 2. SEM and (c,d)
(c,d) CSAC,
CSAC,(e,f)
(e,f)TEM
TEMimages
imagesofofCSAC
CSACatatdifferent
differentmagnifica-
magnifi-
cations and
tions and diffraction
diffraction fringes
fringes in in
thethe selected
selected area
area electron
electron diffraction.
diffraction.

The N22 physisorption

The physisorption isotherms
isotherms of of CSC
CSC and
and CSAC
CSAC areare presented
presented in in Figure
Figure 3a.
3a. Ini-
Ini-
tially, it
tially, it appears
appears thatthat both
both CSC
CSC andand CSAC
CSAC possess
possess copious
copious micropores
micropores leveraging
leveraging the the
steep absorption
steep absorption of of nitrogen
nitrogen under
under the
the relative
relative pressure
pressure ofof 0.05.
0.05. Additionally,
Additionally, the the middle
middle
relative pressure
relative pressure region
region of of the
the CSAC
CSAC isotherm
isotherm exhibits
exhibits greater
greater adsorption
adsorption and and desorption
desorption
platforms, indicating that KOH activation increases the CSAC sample’s
platforms, indicating that KOH activation increases the CSAC sample’s specific surface specific surface area
to 2228 m 2 g−1 . According to IUPAC classification, the adsorption–desorption isotherm
area to 2228 m g . According to IUPAC classification, the adsorption–desorption iso-
2 −1

of CSCofappears
therm to be type-I
CSC appears to becurve,
type-Iwhereas the CSAC
curve, whereas theisotherm exhibits exhibits
CSAC isotherm type-IV features
type-IV
features with a typical H2 hysteresis loop in the relative pressure rangeInofCSAC,
with a typical H2 hysteresis loop in the relative pressure range of 0.4–1.0. such
0.4–1.0. In
a hysteresis loop is assigned to a mesopore feature, which is further
CSAC, such a hysteresis loop is assigned to a mesopore feature, which is further verifiedverified by the pore
sizethe
by distribution. Following KOH
pore size distribution. activation,
Following KOHthere is a noticeable
activation, there is increase in pore
a noticeable volume
increase in
within the range of 0.4 to 5 nm, as seen in Figure 3b. Delving into further
pore volume within the range of 0.4 to 5 nm, as seen in Figure 3b. Delving into further detail, the values
tabulated
detail, the in Tabletabulated
values 1 indicate inan increase
Table in total
1 indicate an pore volumes
increase in totaland micropore
pore volumesvolumes
and mi-
from 0.19 and 0.15 cm 3 g−1 for CSC to 1.07 and 0.64 cm3 g−1 for CSAC. This enhance-
cropore volumes from 0.19 and 0.15 cm3 g−1 for CSC to 1.07 and 0.64 cm3 g−1 for CSAC.
ment can be primarily ascribed to the activation reaction of KOH with coconut shell at
This enhancement can be primarily ascribed to the activation reaction of KOH with coco-
elevated temperatures. This process not only generates a greater number of micropores but
nut shell at elevated temperatures. This process not only generates a greater number of
also fosters the evolution of these micropores into mesopores. Consequently, such micro-,
micropores but also fosters the evolution of these micropores into mesopores. Conse-
meso- and macropores characterized by N2 physisorption and SEM together formed the
quently, such micro-, meso- and macropores characterized by N2 physisorption and SEM
honeycomb-like hierarchical porous architecture, which facilitates swift ion transportation
together formed the honeycomb-like hierarchical porous architecture, which facilitates
from the electrolyte to the adsorption site on the surface of internal micropores.
swift ion transportation from the electrolyte to the adsorption site on the surface of inter-
The wide-scan XPS survey spectra, as depicted in Figure 4a, confirm the main com-
nal micropores.
position of the C (284.5 eV) and O (531.6 eV) species in CSC and CSAC samples, which is
attributed to the predominance of cellulose and lignin in the coconut shell. As evident in
Table 1, the surface status was noticeably affected by the KOH activation. As a result of this
KOH activation at a high temperature, there is a substantial increase in the C content, from
81.02 at.% for CSC to 88.08 at.% for CSAC. The high-resolution spectra are further presented
in Figure 4b for C 1s and Figure 4c for O 1s. High-resolution C 1s spectra exhibit three
resolved peaks located at 284.4, 285.7 and 288.5 eV, correspondingly associated with the
C−C/C=C (C-1), C−O (C-2) and O−C=O (C-3) groups [35]. In terms of the deconvoluted
O 1s region, three fitted peaks are distinguished at 531.4 eV, 532.6 eV and 533.6 eV, which
are credited to quinone oxygen (O-1), phenol groups (O-2) and carboxyl groups (O-3) [36].
Even though the oxygen content is not as abundant as in CSC, CSAC exhibits more exposed
oxygen sites on its surface due to an ample specific surface area (2228 m2 g−1 ). Such oxygen
Molecules 2023, 28, 7187 5 of 14

Figure 3. (a) N2 physisorption isotherms and (b) pore size distributions of CSC and CSAC.

Molecules 2023, 28, x FOR PEER REVIEW

Table 1. Pore
groups characteristics,
on the surface elemental
surface effectively compositions
hasten the and capacitances
electrochemical of CSC and
storage activities 5 of
byCSAC a. 14
enabling
electron transfer and providing additional pseudocapacitance.
Samples SBET (m2 g−1) Vtotal (cm3 g−1) Vmicro (cm3 g−1) C (at.%) O (at.%) Ct (F g−1) CE (F g−1) CP (F g−1)
CSC 204 0.19 0.15 81.82 18.18 121 87 34
CSAC 2228 1.07 0.64 88.08 11.92 367 314 53
a SBET, specific surface area; Vtotal, the total pore volume calculated from the Density Functional The-

ory (DFT) method; Vmicro, the pore volume of the micropores; Ct, the total electrochemical capaci-
tance at 0.2 A g−1 tested in two-electrode system using KOH electrolyte; CE, electric double-layer
capacitance; CP, pseudocapacitance.

The wide-scan XPS survey spectra, as depicted in Figure 4a, confirm the main com-
position of the C (284.5 eV) and O (531.6 eV) species in CSC and CSAC samples, which is
attributed to the predominance of cellulose and lignin in the coconut shell. As evident in
Table 1, the surface status was noticeably affected by the KOH activation. As a result of
this KOH activation at a high temperature, there is a substantial increase in the C content,
from 81.02 at.% for CSC to 88.08 at.% for CSAC. The high-resolution spectra are further
Figure 3. (a)
presented inNFigure
22 physisorption
4b for C isotherms
physisorption 1s and Figure and (b) 4c pore
for Osize
1s. distributions
High-resolution of CSC C 1sandspectra
CSAC. exhibit
three resolved peaks located at 284.4, 285.7 and 288.5 eV, correspondingly associated with
Table
the
Table 1. Pore
C−C/C=C
1. Pore characteristics,
characteristics,
(C-1), C−O (C-2) surface
surface andelemental
O−C=O compositions
elemental (C-3) groupsand
compositions [35].
and capacitances
In terms of
capacitances ofofCSC
the
CSC and
andCSAC
CSAC. a .
deconvoluted
a

Samples SBET (m2 g−1) O (cm

Vtotal 1s region,
3 g−1) threeVmicro fitted
(cm3 3gpeaks
−1) are distinguished
C (at.%) O (at.%) at 531.4CeV, 532.6 eVCEand
t (F g−1) (F g533.6
−1) eV,
C which
P (F g−1)
Samples SBET (m2 g−1 ) Vare (cm3 g−1 ) to quinone
total credited g−1 ) (O-1),
V micro (cmoxygen C (at.%)
phenolOgroups (at.%)
(O-2)Ct (F g−1 )
and carboxyl CE (F g−1 ) CP (F g−1 )
groups (O-3) [36].
CSC
CSC
204
204
0.190.19
0.15
0.15
81.82
81.82
18.18
18.18
121
121
87
87
34
34
Even though the oxygen content is not as abundant as in CSC, CSAC exhibits more ex-
CSAC
CSAC 2228
2228 1.071.07 0.64
0.64 88.08
88.08 11.92
11.92 367
367 314
314 53
53
posed oxygen sites on its surface due to an ample specific surface area (2228 m2 g−1). Such
aa S BET , specific surface area; V total , the total pore volume calculated from the Density
SBET , specific surface area; V total , the total pore volume calculated from the Density Functional Theory (DFT) Functional The-
oxygen
ory (DFT)
method;
groups
method;
V micro
onVthe
, the pore
surface
, the of
volume
micro pore
effectively
the volume
micropores;
hasten
of the
the electrochemical
micropores;
Ct , the Ct, the total
total electrochemical
storage
electrochemical
capacitance
activities
at 0.2 A g−capaci-
byin
1 tested
enabling
two-electrode electron
tance at 0.2 Asystem g tested
−1 transfer
usingin KOH and providing
electrolyte; Csystem
two-electrode additional
E , electric
pseudocapacitance.
double-layer
using capacitance;
KOH electrolyte; CEC,Pelectric
, pseudocapacitance.
double-layer
capacitance; CP, pseudocapacitance.

The wide-scan XPS survey spectra, as depicted in Figure 4a, confirm the main com-
position of the C (284.5 eV) and O (531.6 eV) species in CSC and CSAC samples, which is
attributed to the predominance of cellulose and lignin in the coconut shell. As evident in
Table 1, the surface status was noticeably affected by the KOH activation. As a result of
this KOH activation at a high temperature, there is a substantial increase in the C content,
from 81.02 at.% for CSC to 88.08 at.% for CSAC. The high-resolution spectra are further
presented in Figure 4b for C 1s and Figure 4c for O 1s. High-resolution C 1s spectra exhibit
three resolved peaks located at 284.4, 285.7 and 288.5 eV, correspondingly associated with
the C−C/C=C (C-1), C−O (C-2) and O−C=O (C-3) groups [35]. In terms of the deconvoluted
O 1s region, three fitted peaks are distinguished at 531.4 eV, 532.6 eV and 533.6 eV, which
are credited
Figure
Figure 4.4.(a) to quinone
(a)XPS
XPS survey oxygen
surveyspectra
spectra of (O-1),
ofCSC
CSCand
andphenol
CSAC.groups
CSAC. (O-2) and
High-resolution
High-resolution carboxyl
spectra
spectraof groups
of(b)
(b)CC1s (O-3)
1sand
and (c) [36].
(c)OO1s.
1s.
Even though the oxygen content is not as abundant as in CSC, CSAC exhibits more ex-
posed Theoxygen sites on itsperformances
electrochemical surface due toofan ample specific
pyrolyzed surface
products area (2228
are initially m2 g−1).inSuch
appraised the
oxygen groups
symmetric on the surface
supercapacitor in 6 Meffectively hasten the
KOH electrolyte electrochemical
at 0–1.0 V. CV profilesstorage
(Figureactivities
5a) andby at
10 mV s−electron
enabling 1 displaytransfer and providing
a quasi-rectangular additional
shape withinpseudocapacitance.
both the CSC and CSAC electrodes,
implying ideal capacitive performance. In addition, CSAC displays a more extensive CV
profile area than CSC, indicating a higher specific capacitance achieved. Figure 5b exhibits
that the CV profiles of the CSAC electrode nearly maintain the rectangular-like shapes from
5 to 100 mV s−1 , illustrating excellent reproducible capacitive behavior. To delve further
into the charge storage kinetics, CV curves of CSC and CSAC were explored at various
scan rates, as in the following Equation (1):

i = k1 v + k2 v1/2 (1)

where k1 v refers to the current density related to a fast kinetic response, which are primarily
surface-dominated, k2 v1/2 equals the current density resulting from slow kinetic processes,
which is mainly associated with the diffusion of ions. As plotted in Figures 5c and S2, the
devices of CSC and CSAC exhibit a fast kinetic capacitance of 90 and 296 F g−1 , respectively.
Figure 4. (a) XPS survey spectra of CSC and CSAC. High-resolution spectra of (b) C 1s and (c) O 1s.
 plored at various scan rates, as in the following Equation (1):
⁄
𝑖=𝑘 𝑣 𝑘 𝑣 (1)
where k1v refers to the current density related to a fast kinetic response, which are primar-
ily surface-dominated, k2v1/2 equals the current density resulting from slow kinetic pro-
Molecules 2023, 28, 7187 cesses, which is mainly associated with the diffusion of ions. As plotted in Figure 5c6 and of 14

Figure S2, the devices of CSC and CSAC exhibit a fast kinetic capacitance of 90 and 296 F
g−1, respectively. The GCD curves of CSC- and CSAC-based devices, performed at 0.5 A
−1 (Figure
gThe GCD curves5d), exhibit a triangle-like
of CSC- and CSAC-based distribution withperformed
devices, a small Ohmic A g−implying
at 0.5drop, 1 (Figure 5d),
op-
timal
exhibit electrical double-layer
a triangle-like capacitive
distribution with characteristics.
a small Ohmic Furthermore,
drop, implying the GCD curves
optimal of
electrical
double-layerdevices
CSAC-based capacitive characteristics.byFurthermore,
are distinguished the GCD
isosceles triangles curves
and good of CSAC-based
linearity at current
devices are
densities distinguished
from 0.2 to 10 Aby g−1isosceles
(Figure triangles
5e), whichand goodwell
align linearity at current
with CV results.densities from
The specific
0.2 to 10 A g −1 (Figure 5e), which align well with CV results. The specific capacitance of
capacitance of a CSAC electrode, derived from discharge curves, reveals an exceptionally
a CSAC
high valueelectrode,
of 367 Fderived from
g−1 at 0.2 A gdischarge curves,
−1 and retains 316 reveals
F g−1 atan 10exceptionally high value of
A g−1. The electrochemical
− 1
367 F g atof0.2 − 1
A gCSCand retains − 1 − 1
properties both and CSAC316 F g at 10
electrodes, A g .from
derived The electrochemical
CV and GCD curves properties
under of
both CSCscan
different andrates/current
CSAC electrodes, derived
densities, from CV and
are tabulated GCDS1.
in Table curves under different
As depicted in Figure scan
5f,
rates/current
the densities, arecapacitance
electrical double-layer tabulated in(CTable S1. As depicted
E) calculated from theinintercept
Figure 5f, the aelectrical
with vertical
double-layer capacitance (C ) calculated from the intercept with a vertical
coordinate gives 314 F g for CSAC and 87 F g for CSC, respectively. A detailed compar-
−1 E −1 coordinate gives
314 F g −1 for CSAC and 87 F g−1 for CSC, respectively. A detailed comparison of C (the
ison of Ct (the total electrochemical capacitance), CE and Cp (pseudocapacitance) are tabu- t
total electrochemical
lated in Table 1. capacitance), CE and Cp (pseudocapacitance) are tabulated in Table 1.

Figure
Figure 5.5. Electrochemistry
Electrochemistry characterizations
characterizationsof
of CSC
CSC and
and CSAC
CSAC electrodes
electrodes tested
tested in
in the
the 66 M
M KOH
KOH
symmetric supercapacitor: (a) CV curves at 10 mV s− −1, (b) CV curves of CSAC at various scan rates,
1
symmetric supercapacitor: (a) CV curves at 10 mV s , (b) CV curves of CSAC at various scan rates,
(c) histogram of the decoupling capacitance contributions of CSAC at various scan rates, (d) GCD
(c) histogram of the decoupling capacitance contributions of CSAC at various scan rates, (d) GCD
curves at 0.5 A g−1 , (e) GCD curves of CSAC at various current densities, (f) specific capacitance vs.
square root of discharge time.

The Nyquist diagrams in Figure 6a illustrate that the CSAC-based device achieves a
much lesser equivalent series resistance (Rs ) of 0.23 Ω as well as charge transfer resistance
(Rct ) of 0.41 Ω than the CSC-based device. According to the related Bode plots (Figure 6b)
and Randles plots (Figure 6c), the relaxation time constant τ value and diffusive resistance
σ value of a CSAC-based device is 0.59 s and 0.24 Ω s−0.5 , respectively, indicating a quick
frequency response and swift access of ions to the internal interaction site. The long-term
cycle life of a CSAC-based device, shown in Figure 6d, reveals excellent electrochemical
stability. The capacitance has decayed from 316 F g−1 to 291 F g−1 (retention of 92.09% with
coulombic efficiency of 93.04%) at the high current density of 10 A g−1 after 10,000 cycles,
highlighting superior reversibility. Figure 6e presents the Radar chart containing six
parameters (specific capacitance, SBET , Vtotal , V micro , Rs and Rct ) for a clear comparison of
the CSC and CSAC samples. Table S2 tabulates the electrochemical properties of CSAC and
other biomass-derived carbons-based symmetric supercapacitors. Reflecting upon all these
 frequency response and swift access of ions to the internal interaction site. The long-term
cycle life of a CSAC-based device, shown in Figure 6d, reveals excellent electrochemical
stability. The capacitance has decayed from 316 F g−1 to 291 F g−1 (retention of 92.09% with
coulombic efficiency of 93.04%) at the high current density of 10 A g−1 after 10,000 cycles,
highlighting superior reversibility. Figure 6e presents the Radar chart containing six pa-
Molecules 2023, 28, 7187 7 of 14
rameters (specific capacitance, SBET, Vtotal, Vmicro, Rs and Rct) for a clear comparison of the
CSC and CSAC samples. Table S2 tabulates the electrochemical properties of CSAC and
other biomass-derived carbons-based symmetric supercapacitors. Reflecting upon all
results, the outstanding
these results, performance
the outstanding of CSAC
performance can becan
of CSAC mainly ascribed
be mainly to one-step
ascribed KOH
to one-step
activation,
KOH activation,which which
not onlynotgenerates the honeycomb-like
only generates morphology
the honeycomb-like with a hierarchical
morphology with a hier-
porous
archicalstructure, enhancing
porous structure, the exposure
enhancing degree ofdegree
the exposure a largeof
surface
a largearea witharea
surface more O active
with more
sites, but itsites,
O active also but
induces a high
it also graphitization
induces with low disordering,
a high graphitization with lowwhich in turn improves
disordering, which in
the
turncharge
improvescarrier
thetransport and conductivity.
charge carrier transport and conductivity.

Figure 6.
Figure 6. Electrochemical
Electrochemical properties
properties of
of CSC
CSC and
and CSAC
CSAC electrodes:
electrodes: (a) Nyquist plots with frequency
frequency
range of
range 1055-0.01 Hz,
of 10 Hz, (b)
(b) Bode
Bode plots,
plots,(c)
(c)Randles
Randlesplots,
plots,(d)
(d)cycling
cyclingstability CSACatat1010AAg−
stabilityofofCSAC 1 and
g−1 and
(e) the comparison Radar chart of six parameters.
(e) the comparison Radar chart of six parameters.

The as-prepared
The as-prepared CSAC
CSAC exhibits
exhibits aa hierarchical
hierarchical porous
porous structure,
structure, large
large specific
specific surface
surface
area and
area and high
high electrical
electrical conductivity,
conductivity, which
which all
all foster
foster greater
greater acceptability
acceptability and
and aa more
more
concise transfer pathway
concise pathway for forelectrolyte
electrolyteions
ionsand
andelectrons.
electrons.Encouraged
Encouraged by by
thethe
above re-
above
remarkable characteristics and 2− (3.79 Å), an aqueous
markable characteristics and thethe small
small hydrated
hydrated radii
radii of 4SO
of SO 2− (3.79
4 Å), an aqueous ZHS
ZHS
devicedevice (Zn//ZnSO
(Zn//ZnSO 4 (aq.)//CSAC)
4(aq.)//CSAC) is furtheris further assembled
assembled to probe into to its
probe into its
practical practical
application.
application. Figurethe
Figure 7a depicts 7a working
depicts the working
principle of principle of a ZHS
a ZHS device. device. from
Benefitting Benefitting from the
the integration
integration of a battery-type anode and supercapacitor-type cathode, the
of a battery-type anode and supercapacitor-type cathode, the energy storage in the ZHSs energy storage in
the ZHSs is mainly through the reversible Zn 2+ deposition/stripping onto the Zn anode
is mainly through the reversible Zn deposition/stripping onto the Zn anode as well as
2+

as well asthe
through through
anion the anion adsorption/desorption
adsorption/desorption on the surfaceon the surface
of the CSAC of cathode.
the CSAC cathode.
Therefore,
Therefore, all electrochemical results reported in Figure 7b–g confirm that a ZHS device
may attain the noted energy and power densities. As depicted in Figure 7b, the CV curves
of the ZHS device show no peaks in oxygen and hydrogen generation at various scan
rates, indicating that the ZHSs can operate well from 0.05 to 1.8 V. Furthermore, these
undesirable rectangular profiles illustrate a varied electrochemical performance of the
CSAC cathode and Zn anode in a ZHS device. Simultaneously, the preceding Equation
(1) was used to quantify the different process-controlled contributions of the ZHSs, where
k1 v refers to capacitive contribution and k2 v1/2 denotes the diffusion contribution. As
illustrated in Figures 7c and S3, the capacitive-driven process provides about 52.83% of
the total storage capacity at the scan rate of 1 mV s−1 . As the scan rate increased to
20 mV s−1 , there was a gradual uptick in the capacitive contribution ratio to 82.89%, while
the diffusion contribution ratio correspondingly declined to 17.11%. This change validates
the capacitive-dominant nature from the CSAC cathode and expedited electrochemical
kinetics at a high scan rate. GCD curves were applied to determine the specific capacity
at varying current densities (Figure 7d). Based on the calculation, the discharge specific
capacities of the ZHSs, when employing the CSAC cathode, reach 153, 125, 110, 98, 84
Molecules 2023, 28, 7187 8 of 14

and 75 mAh g−1 at current densities of 0.2, 0.5, 1, 2, 5 and 10 A g−1 . This performance
led to a capacity retention of 49%. Encouragingly, as depicted in Figure 7e, the capacity
in terms of rate performance reverted to 140 mAh g−1 after 120 cycles at a reset current
of 0.2 A g−1 , indicating an excellent reversibility of the ZHSs. Additionally, near-linearity
without a notable potential plateaus feature in GCD curves suggests both electrochemical
double-layer capacitive and pseudocapacitive mechanisms in a hybrid device. Figure 7f
displays the Ragone plots for both symmetric and hybrid supercapacitors. The KOH-loaded
symmetric device of CSAC exhibits an energy density of 12.75 Wh kg−1 at a power density
of 100 W kg−1 [37–39]. Inspired by the outstanding capacity and wide potential window, a
greater energy density of 134.9 Wh kg−1 was achieved by the ZHSs at a power density of
175 W kg−1 . Even more specifically, CSAC-based ZHSs still retained an energy density of
62.6 Wh kg−1 at an ultrahigh power density of 8750 W kg−1 . As presented in Figure 7g, a
high specific capacity of 70 mAh g−1 was obtained at 10 A g−1 after 10,000 cycles, coupled
with 93.81% capacity retention and high coulombic efficiency. Nyquist plots of CSAC-
based ZHSs depicted in Figure S4 exhibit relatively low Rs (2.23 Ω) and Rct (10.22 Ω)
values. The exceptional electrochemical performance of the CSAC cathode-based ZHS
device, in comparison to various ZHS devices as reported in Table 2, can be primarily
attributed to the unique characteristics of a CSAC [40–51]. This includes its honeycomb-like
Molecules 2023,morphology, hierarchical porous structure, large specific surface area, suitable O content
28, x FOR PEER REVIEW 9 of 14
and high conductivity, which collectively enhance ion diffusion and electron transport.

Figure 7. (a) Configuration and working mechanism of ZHS. Electrochemical performance of ZHS
Figure 7. (a) Configuration and working mechanism of ZHS. Electrochemical performance of ZHS
based on CSAC cathode, (b) CV curves at various scan rates, (c) the capacitive and diffusion contri-
based on CSAC cathode, (b) CV
bution ratios curves
to the total at various
capacity at scan rates,
various scan(c) the (d)
rates, capacitive and diffusion
galvanostatic contri- profiles
charge–discharge
bution ratios to the
at total capacity
various current at various(e)
densities, scan
raterates, (d) galvanostatic
performance, charge–discharge
(f) Ragone plots profiles
[14,37–39,45–51] and (g) cycling
at various currentperformance at rate
densities, (e) g−1.
10 A performance, (f) Ragone plots [14,37–39,45–51] and (g) cycling
performance at 10 A g−1 .
Table 2. Electrochemical performance comparison of aqueous ZHSs based on different cathodes b.

Cathode Materials Electrolyte V (V) Clc (mAh g−1) Chc (mAh g−1) E (Wh kg−1) Ref.
CSAC 1 M ZnSO4 0.05–1.8 152 (0.2 A g−1) 75 (10 A g−1) 134.9 This work
BN-LDC 1 M ZnSO4 0.2–1.8 127.7 (0.5 A g−1) 42.8 (10 A g−1) 97.6 [40]
PANI 2 M ZnCl2 0.7–1.7 142.3 (0.2 A g−1) 81.1 (4 A g−1) 117.5 [41]
Molecules 2023, 28, 7187 9 of 14

Table 2. Electrochemical performance comparison of aqueous ZHSs based on different cathodes b .

Cathode
Electrolyte V (V) Clc (mAh g−1 ) Chc (mAh g−1 ) E (Wh kg−1 ) Ref.
Materials
CSAC 1 M ZnSO4 0.05–1.8 152 (0.2 A g−1 ) 75 (10 A g−1 ) 134.9 This work
BN-LDC 1 M ZnSO4 0.2–1.8 −
127.7 (0.5 A g ) 1 42.8 (10 A g−1 ) 97.6 [40]
PANI 2 M ZnCl2 0.7–1.7 142.3 (0.2 A g−1 ) 81.1 (4 A g−1 ) 117.5 [41]
AC 2 M ZnSO4 0.2–1.8 121.0 (0.1 A g−1 ) 41.0 (1 A g−1 ) 84 [42]
OPCNF-20 1 M ZnSO4 0.2–1.8 136.4 (0.1 A g−1 ) 38.7 (20 A g−1 ) 97.7 [43]
HNPC 1 M ZnSO4 0–1.8 177.8 (4.2 A g−1 ) 108.2 (33.3 A g−1 ) 107.3 [44]
TFMA 2 M ZnSO4 0.1–1.8 −
107.0 (1 A g ) 1 53 (10 A g−1 ) 110.8 [45]
C-0.6 2 M ZnSO4 0.2–1.8 181.7 (0.05 A g−1 ) 66.7 (20 A g−1 ) 145.2 [46]
HPCS-900 2 M ZnSO4 0.1–1.7 104.7 (0.1 A g−1 ) 40.2 (20 A g−1 ) 90.2 [47]
CSGC
Molecules 2 M ZnSO
2023, 28, x FOR PEER 4
REVIEW 0.2–1.8 138.8 (0.1 A g−1 ) 85.6 (20 A g−1 ) 111.1 [48]
10 of 14
N-HHPC 2 M ZnSO4 0.1–1.8 140.7 (0.2 A g−1 ) 101.3 (100 A g−1 ) 130.2 [49]
AC-CS 1 M Zn(CF3 SO3 ) 0–1.8 85.7 (0.1 A g−1 ) 38.1 (2 A g−1 ) 52.7 [50]
NPC 1 M ZnSO4 0–1.8 −
136.2 (0.3 A g ) 1 69.2 (15 A g−1 ) 81.1 [51]
b V, the practical working voltage; Clc, the specific capacity at low specific current; Chc, the specific
b V, the practical working voltage; C , the specific capacity at low specific current; C , the specific capacity at
lc hc
capacity at high
high specific specific
current; E, the current; E, the energy density.
energy density.

3.
3. Materials
Materials and
and Methods
Methods
3.1. Preparation of Coconut Shell-Derived Activated Carbon
Coconut shells
shellswere
weresourced
sourcedfrom froma local
a local fruit
fruit market
market nearnear Jiujiang
Jiujiang University.
University. Ini-
Initially,
tially, these shells
these shells were chopped
were chopped into small
into small fragments
fragments and thoroughly
and thoroughly cleaned
cleaned to remove
to remove the
the residual
residual dust.
dust. TheThe fragments
fragments were
were then
then oven-driedatat6060◦ C
oven-dried °Cfor
for48
48h,h, after
after which they
were ground intointo powder.
powder. This
Thisobtained
obtainedcoconut
coconutshell shellpowder
powderwaswasmixed
mixedwithwithKOH
KOH inina
a weight ratio of 1:1, and then activated at 800 ◦ C for 2 h under a nitrogen atmosphere,
weight ratio of 1:1, and then activated at 800 °C for 2 h under a nitrogen atmosphere,
maintaining a heating rate of of 22 ◦°C min−−11.. The
C min The resulting
resulting mixture
mixture was
was washed
washed with dilute
HCl and
and deionized
deionizedwater
wateruntil
untilititreached
reacheda apH pHofof 7, 7,
and andthen oven-dried
then oven-driedovernight at ◦60
at 60
overnight C
○
to
C yield thethe
to yield coconut
coconutshell-derived
shell-derived activated
activated carbon
carbon (denoted as CSAC).
(denoted as CSAC).ForFor
comparison,
compari-
the coconut
son, shell-derived
the coconut carbon
shell-derived (abbreviated
carbon as CSC)
(abbreviated aswas also
CSC) prepared
was withoutwithout
also prepared adding
KOH, following the same procedure. Figure 8 provides a schematic
adding KOH, following the same procedure. Figure 8 provides a schematic diagram de- diagram depicting the
CSAC preparation process and its subsequent application in supercapacitors.
picting the CSAC preparation process and its subsequent application in supercapacitors.

Figure 8. Schematic diagram for preparing CSAC and its application in supercapacitors.

3.2. Characterization
3.2. Characterization
An STA800
An STA800 thermogravimetric
thermogravimetric analyzer
analyzer (PerkinElmer,
(PerkinElmer, Waltham,
Waltham, MA,MA, USA)
USA) was
was em-
em-
ployed to
ployed to perform
performthe thethermogravimetric
thermogravimetricanalysis
analysisofof
coconut shell
coconut from
shell room
from temperature
room tempera-
to 900 ◦ C under nitrogen with a heating rate of 5 ◦ C min−1−1. The compositional phases
ture to 900 °C under nitrogen with a heating rate of 5 °C min . The compositional phases
and crystallographic structure of the carbon samples were examined by the XRD patterns
and crystallographic structure of the carbon samples were examined by the XRD patterns
generated by a Bruker Focus D8 Advance diffractometer (Karlsruhe, Germany) with Cu Kα
generated by a Bruker Focus D8 Advance diffractometer (Karlsruhe, Germany) with Cu
radiation (λ = 1.54 Å). Raman spectra were procured with a Renishaw Inviaspectrometer
Kα radiation (λ = 1.54 Å). Raman spectra were procured with a Renishaw Inviaspectrom-
(London, British), using an excitation wavelength of 532 nm, an excitation power of 1.5 mW
eter (London, British), using an excitation wavelength of 532 nm, an excitation power of
and an acquisition time of 55 s. The surface structures and morphology characterizations of
1.5 mW and an acquisition time of 55 s. The surface structures and morphology character-
carbon samples were visualized by an S-4800 field-emission scanning electron microscope
izations of carbon samples were visualized by an S-4800 field-emission scanning electron
(SEM, Tokyo, Japan) and JEOL JEM-2100 transmission electron microscope (TEM, Tokyo,
microscope (SEM, Tokyo, Japan) and JEOL JEM-2100 transmission electron microscope
Japan), while the coconut shell was observed with an SZ810 optical microscope (OPTEC,
(TEM, Tokyo, Japan), while the coconut shell was observed with an SZ810 optical micro-
Chongqing, China). The samples were degassed at 200 ◦ C for 2 h, and then tested on a
scope (OPTEC, Chongqing, China). The samples were degassed at 200 °C for 2 h, and then
tested on a Micromeritics ASAP 2460 analyzer (Norcross, GA, USA) at −196 °C to obtain
the nitrogen physisorption isotherms. The specific surface areas were evaluated from the
Brunauer–Emmett–Teller (BET) method, and the pore size distributions were calculated
based on the nonlocal density functional theory (DFT) model. The surface chemical com-
Molecules 2023, 28, 7187 10 of 14

Micromeritics ASAP 2460 analyzer (Norcross, GA, USA) at −196 ◦ C to obtain the nitrogen
physisorption isotherms. The specific surface areas were evaluated from the Brunauer–
Emmett–Teller (BET) method, and the pore size distributions were calculated based on the
nonlocal density functional theory (DFT) model. The surface chemical compositions were
detected by an AXIS Ultra DLD X-ray photoelectron spectrometer (XPS, Shimadzu, Kyoto,
Japan) equipped with Al Kα radiation. All samples charging were calibrated using the C 1s
peak (284.4 eV) as an internal standard.

3.3. Electrochemical Measurements

All electrochemical performances of carbon samples were evaluated using CR2032
coin-type cells. For symmetric supercapacitors, a homogeneous slurry was created by
combining the as-prepared carbon, acetylene black and polytetrafluoroethylene (PTFE) in
ethanol and N-methyl-2-pyrrolidinone (NMP) solution at a ratio of 8:1:1. The working
electrode was then created by pressing the dry slurry under 15 MPa on nickel foam. A
single electrode had approximately 2 mg cm−2 active material. Two identical working
electrodes were assembled in the 6 M KOH-loaded symmetric supercapacitor, where a piece
of filter paper was applied as a separator. The electrochemical measurements, compris-
ing cyclic voltammetry (CV), galvanostatic charge–discharge (GCD) and electrochemical
impedance spectroscopies (EIS), were conducted on a coin-type device using a Chenhua
electrochemical workstation (CHI660D, Shanghai, China). The specific capacitance (C,
F g−1 ) of the individual electrode in the symmetric supercapacitor was determined based
on the CV and GCD curves, according to the following Equations (2) and (3):
R
idV
CCV = 4 × (2)
2 × ∆V × m × r

I × ∆t
CGCD = 4 × (3)
∆V × m
where ∆V (V) is the operation potential window, r (V s−1 ) is the scan rate, m (g) is the total
mass of both electrodes and ∆t (s) is the discharging time. i (A) in Equation (2) and I (A) in
Equation (3) is the response current and the discharging current, respectively.
The ZHSs were also assembled in a CR2032 coin cell, employing zinc foil (12 mm in
diameter), 1 M ZnSO4 solution and a glass fiber membrane as the anode, the electrolyte
and the separator, respectively. The CSAC cathode electrode included a CSAC powder
(80 wt.%), conductive acetylene black (10 wt.%) and poly(vinylidene fluoride) (PVDF,
10 wt.%). N-methyl-2-pyrrolidinone (NMP) solution was added to this mixture to form a
uniform slurry. This was then coated on stainless steel foil and subsequently dried in a
vacuum oven at 60 ◦ C for 24 h. The CV and EIS measurements of ZHS were conducted on a
Chenhua electrochemical workstation, while the GCD and long circles tests were evaluated
by a CT2001 battery testing system (LAND, Wuhan, China).

4. Conclusions
In summary, we have successfully synthesized a hierarchical porous activated carbon
from coconut shells via one-step KOH activation. The resultant CSAC materials feature
exceptional properties including a honeycomb-like morphology, hierarchical porous struc-
ture, large specific surface area and commendable electrical conductivity. Thanks to these
distinct advantages, a CSAC electrode manifests superior electrochemical performances in
symmetric and hybrid supercapacitors. An ultrahigh specific capacitance of 367 F g−1 was
achieved by a CSAC electrode in a 6 M KOH loaded-symmetric supercapacitor, maintaining
92.09% capacity retention even after 10,000 cycles at 10 A g−1 . More notably, the ZHSs
using CSAC as a cathode achieve a high-rate capability (153 mAh g−1 at 0.2 A g−1 and
75 mAh g−1 at 10 A g−1 ), high energy density (134.9 Wh kg−1 at 175 W kg−1 ), as well as
outstanding cycling stability (93.81% capacity retention after 10,000 cycles at 10 A g−1 ). Pos-
sessing excellent energy storage performance affirms that coconut shell-derived HPAC is a
Molecules 2023, 28, 7187 11 of 14

prospective candidate in ultrahigh-performance supercapacitors for industrial large-scale

applications.

Supplementary Materials: The following supporting information can be downloaded at: https://
www.mdpi.com/article/10.3390/molecules28207187/s1. Refs. [52–66] are cite in the Supplementary
Materials.
Author Contributions: Conceptualization, H.H. (Huanan Hu); data curation, Y.D. and X.L.; formal
analysis, Y.W., Y.D., L.S., R.W. and H.H. (Huanan Huang); funding acquisition, Y.W. and P.Y.; in-
vestigation, Y.D.; methodology, Y.W., Y.D., X.L., L.T., L.S. and R.W.; project administration, Y.W.,
P.Y. and H.H. (Huanan Hu); software, Y.D., X.L. and L.T.; supervisions, Y.W. and H.H. (Huanan
Hu); validation, S.W., P.Y.; writing—original draft, Y.W.; writing—review and editing, Y.W. and H.H.
(Huanan Hu). All authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the National Natural Science Foundation of China
(NO. 52062023), Jiangxi Provincial Natural Science Foundation (NO. 20232BAB203045, 20202BABL203028),
the Education Department of Jiangxi Province Foundation of China (No. GJJ2201912) and the Training
Program of Innovation and Entrepreneurship for Undergraduates (202111843011).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors would like to thank Shiyanjia Lab (www.shiyanjia.com (accessed
on 22 November 2022)) for the support for the XPS and SEM tests. Finally, the authors thank Jialei Du
from University of Jinan for the project administration in this work.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Not applicable.

References
1. Arico, A.S.; Bruce, P.; Scrosati, B.; Tarascon, J.M.; Van Schalkwijk, W. Nanostructured materials for advanced energy conversion
and storage devices. Nat. Mater. 2005, 4, 366–377. [CrossRef] [PubMed]
2. Han, S.A.; Qutaish, H.; Lee, J.W.; Park, M.S.; Kim, J.H. Metal-organic framework derived porous structures towards lithium
rechargeable batteries. EcoMat 2023, 5, 12283. [CrossRef]
3. Shao, H.; Wu, Y.C.; Lin, Z.F.; Taberna, P.L.; Simon, P. Nanoporous carbon for electrochemical capacitive energy storage. Chem. Soc.
Rev. 2020, 49, 3005–3039. [CrossRef] [PubMed]
4. Simon, P.; Gogotsi, Y. Perspectives for electrochemical capacitors and related devices. Nat. Mater. 2020, 19, 1151–1163. [CrossRef]
5. Wang, G.P.; Zhang, L.; Zhang, J.J. A review of electrode materials for electrochemical supercapacitors. Chem. Soc. Rev. 2012, 41,
797–828. [CrossRef]
6. Miao, L.; Song, Z.Y.; Zhu, D.Z.; Li, L.C.; Gan, L.H.; Liu, M.X. Ionic liquids for supercapacitive energy storage: A mini-review.
Energ. Fuel. 2021, 35, 8443–8455. [CrossRef]
7. Song, Z.Y.; Miao, L.; Ruhlmann, L.; Lv, Y.K.; Zhu, D.Z.; Li, L.C.; Gan, L.H.; Liu, M.X. Self-assembled carbon superstructures
achieving ultra-stable and fast proton-coupled charge storage kinetics. Adv. Mater. 2021, 33, e2104148. [CrossRef] [PubMed]
8. Augustyn, V.; Simon, P.; Dunn, B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energ. Environ.
Sci. 2014, 7, 1597–1614. [CrossRef]
9. Muzaffar, A.; Ahamed, M.B.; Deshmukh, K.; Thirumalai, J. A review on recent advances in hybrid supercapacitors: Design,
fabrication and applications. Renew. Sust. Energ. Rev. 2019, 101, 123–145. [CrossRef]
10. Yan, J.; Li, S.H.; Lan, B.B.; Wu, Y.C.; Lee, P.S. Rational design of nanostructured electrode materials toward multifunctional
supercapacitors. Adv. Funct. Mater. 2020, 30, 1902564. [CrossRef]
11. Noori, A.; El-Kady, M.F.; Rahmanifar, M.S.; Kaner, R.B.; Mousavi, M.F. Towards establishing standard performance metrics for
batteries, supercapacitors and beyond. Chem. Soc. Rev. 2019, 48, 1272–1341. [CrossRef] [PubMed]
12. Shao, Y.L.; El-Kady, M.F.; Sun, J.Y.; Li, Y.G.; Zhang, Q.H.; Zhu, M.F.; Wang, H.Z.; Dunn, B.; Kaner, R.B. Design and mechanisms of
asymmetric supercapacitors. Chem. Rev. 2018, 118, 9233–9280. [CrossRef] [PubMed]
13. Wang, Y.W.; Hao, L.N.; Zeng, Y.; Cao, X.H.; Huang, H.N.; Liu, J.H.; Chen, X.D.; Wei, S.H.; Gan, L.H.; Yang, P.H.; et al. Three-
dimensional hierarchical porous carbon derived from resorcinol formaldehyde-zinc tatrateipoly(styrene-maleic anhydride) for
high performance supercapacitor electrode. J. Alloys Compd. 2021, 886, 161176. [CrossRef]
Molecules 2023, 28, 7187 12 of 14

14. Wang, Y.W.; Zeng, Y.; Zhu, J.B.; Yang, C.; Huang, H.A.; Chen, X.D.; Wang, R.R.; Yan, P.; Wei, S.H.; Liu, M.X.; et al. From
dual-aerogels with semi-interpenetrating polymer network structure to hierarchical porous carbons for advanced supercapacitor
electrodes. Colloid. Surface. A 2022, 649, 129356. [CrossRef]
15. Yin, J.; Zhang, W.L.; Alhebshi, N.A.; Salah, N.; Alshareef, H.N. Synthesis strategies of porous carbon for supercapacitor
applications. Small Methods 2020, 4, 1900853. [CrossRef]
16. Wang, J.C.; Kaskel, S. KOH activation of carbon-based materials for energy storage. J. Mater. Chem. 2012, 22, 23710–23725.
[CrossRef]
17. Meng, Y.; Gu, D.; Zhang, F.Q.; Shi, Y.F.; Yang, H.F.; Li, Z.; Yu, C.Z.; Tu, B.; Zhao, D.Y. Ordered mesoporous polymers and
homologous carbon frameworks: Amphiphilic surfactant templating and direct transformation. Angew. Chem. Int. Edit. 2005, 44,
7053–7059. [CrossRef]
18. Wang, H.; Niu, H.T.; Wang, H.J.; Wang, W.Y.; Jin, X.; Wang, H.X.; Zhou, H.; Lin, T. Micro-meso porous structured carbon nanofibers
with ultra-high surface area and large supercapacitor electrode capacitance. J. Power Sources 2021, 482, 228986. [CrossRef]
19. Wang, Q.; Yan, J.; Wang, Y.B.; Wei, T.; Zhang, M.L.; Jing, X.Y.; Fan, Z.J. Three-dimensional flower-like and hierarchical porous
carbon materials as high-rate performance electrodes for supercapacitors. Carbon 2014, 67, 119–127. [CrossRef]
20. Lu, W.; Cao, X.; Hao, L.; Zhou, Y.; Wang, Y. Activated carbon derived from pitaya peel for supercapacitor applications with high
capacitance performance. Mater. Lett. 2020, 264, 127339. [CrossRef]
21. Qu, W.H.; Xu, Y.Y.; Lu, A.H.; Zhang, X.Q.; Li, W.C. Converting biowaste corncob residue into high value added porous carbon for
supercapacitor electrodes. Bioresour. Technol. 2015, 189, 285–291. [CrossRef] [PubMed]
22. Li, J.T.; Xiao, R.; Li, M.; Zhang, H.Y.; Wu, S.L.; Xia, C.L. Template-synthesized hierarchical porous carbons from bio-oil with high
performance for supercapacitor electrodes. Fuel Process. Technol. 2019, 192, 239–249. [CrossRef]
23. Wang, Y.; Lu, W.; Xu, X.; Pang, F.; Feng, X.; Zhang, X.; Zeng, Y.; Yang, Z.; Wang, R.; Yang, P.; et al. Ternary-doped hierarchical
porous carbons derived from durian kernel as electrode materials for efficient energy storage devices. Diam. Relat. Mater. 2022,
130, 109451. [CrossRef]
24. Xu, X.H.; Sun, S.C.; Luo, J.; Ma, R.; Lin, J.H.; Fang, L.; Zhang, P.X.; Chen, Y. Few-layer graphene prepared via microwave
irradiation of black sesame for supercapacitor applications. Chem. Eng. J. 2021, 425, 130664. [CrossRef]
25. Shen, Y.F. A review on hydrothermal carbonization of biomass and plastic wastes to energy products. Biomass Bioenerg. 2020, 134,
105479. [CrossRef]
26. Yang, Z.H.; Cao, J.P.; Zhuang, Q.Q.; Wu, Y.; Zhou, Z.; Wei, Y.L.; Zhao, X.Y. Oxygen-enriched porous carbon derived from acid
washed and oxidized lignite via H3 PO4 hydrothermal for high-performance supercapacitors. Fuel Process. Technol. 2023, 243,
107665. [CrossRef]
27. Wang, B.; Li, Y.G.; Gu, Z.J.; Wang, H.D.; Liu, X.F.; Li, S.P.; Chen, X.X.; Liang, X.H.; Jiang, Z.X.; Ogino, K.; et al. Synthesis and
design of biomass-derived heteroatom-doped hierarchical porous carbon systems for high-voltage supercapacitors. Fuel Process.
Technol. 2023, 247, 107776. [CrossRef]
28. Yu, P.F.; Zeng, Y.; Zeng, Y.X.; Dong, H.W.; Hu, H.; Liu, Y.L.; Zheng, M.T.; Xiao, Y.; Lu, X.H.; Liang, Y.R. Achieving high-energy-
density and ultra-stable zinc-ion hybrid supercapacitors by engineering hierarchical porous carbon architecture. Electrochim. Acta
2019, 327, 134999. [CrossRef]
29. Javed, M.S.; Najam, T.; Hussain, I.; Idrees, M.; Ahmad, A.; Imran, M.; Shah, S.S.A.; Luque, R.; Han, W.H. Fundamentals and
scientific challenges in structural design of cathode materials for zinc-ion hybrid supercapacitors. Adv. Energy Mater. 2023, 13,
2202303. [CrossRef]
30. Li, Z.W.; Chen, D.H.; An, Y.F.; Chen, C.L.; Wu, L.Y.; Chen, Z.J.; Sun, Y.; Zhang, X.G. Flexible and anti-freezing quasi-solid-state zinc
ion hybrid supercapacitors based on pencil shavings derived porous carbon. Energy Storage Mater. 2020, 28, 307–314. [CrossRef]
31. Lou, G.B.; Pei, G.; Wu, Y.T.; Lu, Y.Z.; Wu, Y.T.; Zhu, X.Q.; Pang, Y.J.; Shen, Z.H.; Wu, Q.; Fu, S.Y.; et al. Combustion conversion of
wood to N, O co-doped 2D carbon nanosheets for zinc-ion hybrid supercapacitors. Chem. Eng. J. 2021, 413, 127502. [CrossRef]
32. Qian, X.Y.; Miao, L.; Jiang, J.X.; Ping, G.C.; Xiong, W.; Lv, Y.K.; Liu, Y.F.; Gan, L.H.; Zhua, D.Z.; Liu, M.X. Hydrangea -like N/O
codoped porous carbons for high-energy supercapacitors. Chem. Eng. J. 2020, 388, 124208. [CrossRef]
33. Wu, X.K.; Yu, M.; Liu, J.H.; Li, S.M.; Zhang, X.L. sp3 -Defect and pore engineered carbon framework for high energy density
supercapacitors. J. Power Sources 2020, 464, 228203. [CrossRef]
34. Wang, H.Y.; Zhao, M.K.; Li, M.R.; Xiao, Q.G.; Shi, H.W.; He, W.; Bian, Z.T.; Zhang, P.H.; Zhu, G.; Chen, C. Three-dimensional
honeycomb-like porous carbon derived from Ganoderma lucidum spore for high-performance electrochemical capacitors. Ionics
2020, 26, 5805–5815. [CrossRef]
35. Teng, W.L.; Zhou, Q.Q.; Wang, X.K.; Gao, J.Y.; Hu, P.; Du, Y.C.; Li, H.Y.; Wang, J.S. Enhancing ions/electrons dual transport in
rGO/PEDOT:PSS fiber for high-performance supercapacitor. Carbon 2022, 189, 284–292. [CrossRef]
36. Gu, Y.Y.; Miao, L.; Yin, Y.; Liu, M.X.; Gan, L.H.; Li, L.C. Highly N/O co-doped ultramicroporous carbons derived from nonporous
metal-organic framework for high performance supercapacitors. Chin. Chem. Lett. 2021, 32, 1491–1496. [CrossRef]
37. Wang, Z.; Tan, Y.T.; Yang, Y.L.; Zhao, X.N.; Liu, Y.; Niu, L.Y.; Tichnell, B.; Kong, L.B.; Kang, L.; Liu, Z.; et al. Pomelo peels-derived
porous activated carbon microsheets dual-doped with nitrogen and phosphorus for high performance electrochemical capacitors.
J. Power Sources 2018, 378, 499–510. [CrossRef]
Molecules 2023, 28, 7187 13 of 14

38. Sheng, Z.; Lin, X.C.; Wei, H.; Zhang, Y.K.; Tian, Z.; Wang, C.H.; Xu, D.P.; Wang, Y.G. Green synthesis of nitrogen-doped hierarchical
porous carbon nanosheets derived from polyvinyl chloride towards high-performance supercapacitor. J. Power Sources 2021,
515, 230629. [CrossRef]
39. Cheng, Y.F.; Li, B.Q.; Huang, Y.J.; Wang, Y.M.; Chen, J.C.; Wei, D.Q.; Feng, Y.J.; Jia, D.C.; Zhou, Y. Molten salt synthesis of nitrogen
and oxygen enriched hierarchically porous carbons derived from biomass via rapid microwave carbonization for high voltage
supercapacitors. Appl. Surf. Sci. 2018, 439, 712–723. [CrossRef]
40. Lu, Y.Y.; Li, Z.W.; Bai, Z.Y.; Mi, H.Y.; Ji, C.C.; Pang, H.; Yu, C.; Qiu, J.S. High energy-power Zn-ion hybrid supercapacitors enabled
by layered B/N co-doped carbon cathode. Nano Energy 2019, 66, 104132. [CrossRef]
41. Ma, Y.; Xie, X.L.; Lv, R.H.; Na, B.; Ouyang, J.B.; Liu, H.S. Nanostructured polyaniline-cellulose papers for solid-state flexibleaque-
ous Zn-ion battery. ACS Sustain. Chem. Eng. 2018, 6, 8697–8703. [CrossRef]
42. Dong, L.B.; Ma, X.P.; Li, Y.; Zhao, L.; Liu, W.B.; Cheng, J.Y.; Xu, C.J.; Li, B.H.; Yang, Q.H.; Kang, F.Y. Extremely safe, high-rate and
ultralong-life zinc-ion hybrid supercapacitors. Energy Storage Mater. 2018, 13, 96–102. [CrossRef]
43. He, H.C.; Lian, J.C.; Chen, C.M.; Xiong, Q.T.; Zhang, M. Super hydrophilic carbon fiber film for freestanding and flexible cathodes
of zinc-ion hybrid supercapacitors. Chem. Eng. J. 2021, 421, 129786. [CrossRef]
44. Zhang, H.Z.; Liu, Q.Y.; Fang, Y.B.; Teng, C.L.; Liu, X.Q.; Fang, P.P.; Tong, Y.X.; Lu, X.H. Boosting Zn-Ion energy storage capability
of hierarchically porous carbon by promoting chemical adsorption. Adv. Mater. 2019, 31, e1904948. [CrossRef]
45. Zhou, S.X.; Li, C.; Gao, G.M.; Fan, H.L.; Hu, X. Bio-based resins with tannin and hydroxymethylfurfural derived high-yield
carbon for Zn-ion hybrid supercapacitors. J. Clean. Prod. 2023, 389, 136067. [CrossRef]
46. Wei, X.; Qiu, B.P.; Tian, H.D.; Lv, Y.H.; Zhang, W.; Qin, Q.Q.; Liu, Z.L.; Wei, F. Co-precipitation reaction: A facile strategy
for designing hierarchical porous carbon nanosheets for EDLCs and zinc-ion hybrid supercapacitors. Appl. Surf. Sci. 2023,
615, 156280. [CrossRef]
47. Shang, K.Z.; Liu, Y.J.; Cai, P.W.; Li, K.K.; Wen, Z.H. N, P, and S co-doped 3D porous carbon-architectured cathode for high-
performance Zn-ion hybrid capacitors. J. Mater. Chem. A 2022, 10, 6489–6498. [CrossRef]
48. Liu, H.; Chen, W.; Peng, H.; Huang, X.L.; Li, S.; Jiang, L.; Zheng, M.Q.; Xu, M.D.; Zhu, J. Bioinspired design of graphene-based
N/O self-doped nanoporous carbon from carp scales for advanced Zn-ion hybrid supercapacitors. Electrochim. Acta 2022, 434,
141312. [CrossRef]
49. Zhou, L.; Yang, Y.; Yang, J.; Ye, P.C.; Ali, T.; Wang, H.Y.; Ning, J.Q.; Zhong, Y.J.; Hu, Y. Achieving fast Zn-ion storage kinetics by
confining nitrogen-enriched carbon nanofragments in a honeycomb-like matrix. Appl. Surf. Sci. 2022, 604, 154526. [CrossRef]
50. Wang, H.; Wang, M.; Tang, Y.B. A novel zinc-ion hybrid supercapacitor for long-life and low-cost energy storage applications.
Energy Storage Mater. 2018, 13, 1–7. [CrossRef]
51. Shi, X.; Zhang, H.Z.; Zeng, S.Q.; Wang, J.; Cao, X.S.; Liu, X.Q.; Lu, X.H. Pyrrolic-dominated nitrogen eedox enhances reaction
kinetics of pitch-derived carbon materials in aqueous zinc ion hybrid supercapacitors. Acs Mater. Lett. 2021, 3, 1291–1299.
[CrossRef]
52. Xia, J.S.; Zhang, N.; Chong, S.K.; Li, D.; Chen, Y.; Sun, C.H. Three-dimensional porous graphene-like sheets synthesized from
biocarbon via low-temperature graphitization for a supercapacitor. Green Chem. 2018, 20, 694–700. [CrossRef]
53. Zhao, Y.; Mu, J.; Wang, Y.; Liu, Y.; Wang, H.; Song, H. Preparation of hierarchical porous carbon through one-step KOH activation
of coconut shell biomass for high-performance supercapacitor. J. Mater. Sci-Mater. El. 2023, 34, 527. [CrossRef]
54. Bora, M.; Bhattacharjya, D.; Hazarika, S.; Fan, X.; Saikia, B.K. Blending of activated low-grade coal powder with coconut shell
waste for supercapacitor applications. Energ. Fuel. 2022, 36, 14476–14489. [CrossRef]
55. Altinci, O.C.; Demir, M. Beyond conventional activating methods, a green approach for the synthesis of biocarbon and its
supercapacitor electrode performance. Energ. Fuel. 2020, 34, 7658–7665. [CrossRef]
56. Rani, M.U.; Nanaji, K.; Rao, T.N.; Deshpande, A.S. Corn husk derived activated carbon with enhanced electrochemical perfor-
mance for high-voltage supercapacitors. J. Power Sources 2020, 471, 228387. [CrossRef]
57. Lian, Y.M.; Ni, M.; Huang, Z.H.; Chen, R.J.; Zhou, L.; Utetiwabo, W.; Yang, W. Polyethylene waste carbons with a mesoporous
network towards highly efficient supercapacitors. Chem. Eng. J. 2019, 366, 313–320. [CrossRef]
58. Senthil, R.A.; Yang, V.K.; Pan, J.Q.; Sun, Y.Z. A green and economical approach to derive biomass porous carbon from freely
available feather finger grass flower for advanced symmetric supercapacitors. J. Energy Storage 2021, 35, 102287. [CrossRef]
59. Zhang, G.X.; Chen, Y.M.; Chen, Y.G.; Guo, H.B. Activated biomass carbon made from bamboo as electrode material for
supercapacitors. Mater. Res. Bull. 2018, 102, 391–398. [CrossRef]
60. Wang, C.J.; Wu, D.P.; Wang, H.J.; Gao, Z.Y.; Xu, F.; Jiang, K. A green and scalable route to yield porous carbon sheets from biomass
for supercapacitors with high capacity. J. Mater. Chem. A 2018, 6, 1244–1254. [CrossRef]
61. Tian, X.; Ma, H.G.; Li, Z.; Yan, S.C.; Ma, L.; Yu, F.; Wang, G.; Guo, X.H.; Ma, Y.Q.; Wong, C.P. Flute type micropores activated
carbon from cotton stalk for high performance supercapacitors. J. Power Sources 2017, 359, 88–96. [CrossRef]
62. Liu, S.B.; Zhao, Y.; Zhang, B.H.; Xia, H.; Zhou, J.F.; Xie, W.K.; Li, H.J. Nano-micro carbon spheres anchored on porous carbon
derived from dual-biomass as high rate performance supercapacitor electrodes. J. Power Sources 2018, 381, 116–126. [CrossRef]
63. Qu, S.S.; Wan, J.F.; Dai, C.C.; Jin, T.Y.; Ma, F.W. Promising as high-performance supercapacitor electrode materials porous carbons
derived from biological lotus leaf. J. Alloys Compd. 2018, 751, 107–116. [CrossRef]
64. Zhao, C.J.; Huang, Y.X.; Zhao, C.H.; Shao, X.X.; Zhu, Z.Q. Rose-derived 3D carbon nanosheets for high cyclability and extended
voltage supercapacitors. Electrochim. Acta 2018, 291, 287–296. [CrossRef]
Molecules 2023, 28, 7187 14 of 14

65. Dong, S.; He, X.J.; Zhang, H.F.; Xie, X.Y.; Yu, M.X.; Yu, C.; Xiao, N.; Qiu, J.S. Surface modification of biomass-derived hard carbon
by grafting porous carbon nanosheets for high-performance supercapacitors. J. Mater. Chem. A 2018, 6, 15954–15960. [CrossRef]
66. Chen, D.; Li, L.; Xi, Y.L.; Li, J.Z.; Lu, M.J.; Cao, J.M.; Han, W. Self-assembly of biomass microfibers into 3D layer-stacking
hierarchical porous carbon for high performance supercapacitors. Electrochim. Acta 2018, 286, 264–270. [CrossRef]

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