Journal of Energy Storage 81 (2024) 110302

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Journal of Energy Storage

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

Research papers

Boosting supercapacitor performance with a cobalt hydroxide in-situ

preparation orange peel biochar flower-like composite
Akhil Pradiprao Khedulkar a, Wan-Ju Yu b, e, Van Dien Dang c, Bidhan Pandit d, Ruey-an Doong e, *
a
Department of Biomedical Engineering and Environmental Sciences, National Tsing Hua University, Hsinchu 30013, Taiwan
b
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 30013, Taiwan
c
Ho Chi Minh City University of Industry and Trade, 140 Le Trong Tan, Tan Phu district, Ho Chi Minh 700000, Vietnam
d
Department of Materials Science and Engineering and Chemical Engineering, Universidad Carlos III de Madrid (UC3M), Avenida de la Universidad 30, 28911 Leganés,
Madrid, Spain
e
Institute of Analytical and Environmental Sciences, National Tsing Hua University, Hsinchu 30013, Taiwan

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

Keywords: In this study, we present a novel composite material known as Cobalt oxide/orange peel-derived biochar
Orange peel biochar (OBC) (CoNF@OBC), which exhibits a distinctive flower-like structure and showcases exceptional potential for high-
Porous structure performance supercapacitors. The CoNF@OBC composite is created by employing Co(OH)2 as a supporting
Eco-friendly supercapacitor
material. The inherent hierarchical and porous structure of CoNF@OBC facilitates efficient flow and dispersion of
Cobalt hydroxide
ions and electrons within the electrolyte. This structural advantage results in shorter diffusion pathways and
enhanced conductivity, rendering CoNF@OBC highly suitable for energy storage applications. Remarkably,
CoNF@OBC demonstrates an ultra-high specific capacitance of 563 F g− 1 at a current density of 1 A g− 1, with an
outstanding capacitance retention of 96 % even after undergoing 10,000 charge-discharge cycles. When inte­
grated into a device, CoNF@OBC yields a specific capacitance of 124 F g− 1. Furthermore, the Ragone plot for the
symmetric device reveals an energy density ranging from 10 to 41 Wh kg− 1, accompanied by power densities
spanning from 811 to 5143 W kg− 1. This remarkable performance highlights the extensive potential of CoN­
F@OBC in practical applications, supported by its long-term cyclic stability of 92 % after 10,000 charge-
discharge cycles. This study underscores the sustainability aspect of utilizing agricultural waste, such as or­
ange peels, as eco-friendly carbon sources. By combining these waste materials with various metal hydroxides for
eco-friendly supercapacitor electrodes, promoting sustainable energy storage solutions.

1. Introduction researchers have sought ways to harness the potential of biomass re­
sources for various purposes, including energy storage devices. Super­
The increasing global energy consumption, driven by rapid techno­ capacitors are getting a lot of attention lately because they're safer and
logical advancements in our progressive society, has raised significant have more power compared to regular energy storage. In today's rapidly
concerns. The overexploitation of natural resources, mounting worries changing world, the pressing issues of rising global energy consumption,
about global warming, and dwindling fuel reserves have collectively led environmental sustainability, and the transition to renewable energy
to a pressing problem: energy scarcity. In response to this crisis, the have made supercapacitors (SCs) a central focus. Supercapacitors (SCs)
development of renewable and environmentally responsible power enable efficient use of renewable energy, enhance electric vehicle per­
systems has emerged as a critical imperative [1–3]. Another urgent formance, and offer compact energy storage for IoT and electronics.
challenge that demands our attention on a global scale today is the They also ensure grid stability and align with eco-friendly, sustainable
surplus of agricultural waste, which poses a grave threat to our energy solutions, promoting a cleaner future [5,6].
ecosystem. Often, this waste is indiscriminately dumped onto fields, Supercapacitors can be broadly categorized into two main types:
potentially altering soil composition and negatively affecting plant electric double-layer capacitors (EDLC) and pseudocapacitors, each
growth [4]. Recognizing the need to address this issue effectively, characterized by distinct charging and storage mechanisms, particularly

* Corresponding author.
E-mail address: [email protected] (R.-a. Doong).

https://doi.org/10.1016/j.est.2023.110302
Received 6 October 2023; Received in revised form 4 December 2023; Accepted 24 December 2023
Available online 12 January 2024
2352-152X/© 2024 Elsevier Ltd. All rights reserved.
A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

in their electrode materials [7]. EDLCs employ carbon-based materials O, S, P) into the carbon network increases electron dispersion density
(e.g., carbon nanotubes, activated carbon) with a large surface area, and active sites without altering the porous material structure [20]. In
facilitating electrostatic energy storage through charge absorption and this study, we present the fabrication of CoNF@OBC composites using
adsorption at the electrode/electrolyte interfaces. In contrast, pseudo­ an environmentally friendly method. Orange peel was transformed into
capacitors utilize metal oxides (e.g., NiO, CoO, FeO, MnO2, MoO2) to activated porous carbon (OBC) with a substantial surface area of 911 m2
achieve pseudo capacitance via reversible surface oxidation-reduction g− 1 through alkali treatment and high-temperature heating. CoNF was
reactions [8]. However, despite notable advancements in both elec­ then grown on the conductive OBC, forming the CoNF@OBC compos­
trode materials, challenges persist. Carbon-based materials exhibit low ites. Our experimental results reveal a remarkable specific capacitance
capacitance values, minimal power density, and relatively poor cycle of 563 F g− 1 at 1 A g− 1 in a three-electrode cell, alongside an exceptional
efficiency, while metal oxides/hydroxides face limitations in conduc­ energy density of 41 Wh kg− 1 and a maximum power density of 811 W
tivity [9,10]. To overcome these limitations, researchers have explored kg− 1 at 1 A g− 1, as illustrated in Fig. 1. Furthermore, this device main­
combining transition metal oxides with carbon-based composites. This tained its performance even after 10,000 cycles, showcasing its long-
synergy addresses the drawbacks of individual components, as the metal term viability. This work opens up exciting prospects for the creation
oxides enhance conductivity, and the carbon provides a high surface of high-end energy storage devices utilizing agricultural waste-based
area, resulting in excellent supercapacitive performance [11,12]. As the biochars, contributing to a greener circular economy.
world strives for sustainable solutions, there is a growing emphasis on
environmentally friendly materials in energy storage systems. Biomass- 2. Experimental
derived materials have emerged as an eco-conscious alternative, offering
unique advantages in terms of renewability and reduced environmental 2.1. Synthesis of hierarchical OBC
impact. One particularly promising source of biomass for such com­
posites is orange peel waste, a byproduct abundant in the citrus industry The orange peel was washed multiple times in warm bi-distilled
[13]. Orange peel has already proven its potential as a precursor for deionized water before being treated with an ultrasonic cleaner to
activated carbon with a large surface area [14]. Moreover, it contains remove contaminants. The cleaned orange peel was dried for 48 h in a
functional groups like carboxyl (–COOH) and amine (–NH2), which hot air oven before being carbonized in Ar for 3 h at 500 ◦ C (rate of 5 ◦ C/
interact favorably with metallic ions, improving capacity and surface min-1). The obtained product was labeled as OBC. The OBC was then
wettability while enhancing conductivity [15]. In previous research, added into 5 M NaOH and aggressively stirred for 3 h. The solid portion
orange peel was successfully employed to create an electrode with a was separated by centrifugation, dried at 60 ◦ C for 96 h, and then py­
specific capacitance of 240 F g− 1, underscoring its potential as a valu­ rolyzed at 850 ◦ C for 2 h. After reaching room temperature, the OBC was
able material [16]. Additionally, low-cost metal oxides, including cobalt cleaned using 0.2 M HNO3 and Distilled water to remove contaminants.
oxide (Co3O4), have gained traction for supercapacitor electrodes due to OBC was then added into 20 mL of 2 M HNO3 and stirred magnetically
their high theoretical capacitance, environmental friendliness, afford­ for 2 h. The solution was inserted to a Teflon tube for the next step,
ability, and physicochemical stability [17]. However, the impact of self- which involved heating it in an oven for 2 h at 150 ◦ C. To get a pH that
doping atoms in carbon derived from biological sources on capacitance, was roughly neutral, the mixture was washed with DI. After being
as well as the anchoring of Co3O4 on the surface interface of carbon picked, the product was dried for the entire night at 90 ◦ C.
derived from biological sources, has not been fully explored [18]. This
combination of Co3O4 and carbon from biomass holds promise, given
2.2. Synthesis of CoNF@OBC
the significant active anchoring positions and strengthened Co–O–C
linkage it provides, ensuring structural stability and good conductivity
1 mg of OBC was added in a solution of 7 mg of (Co(NO3)2) and 4 mL
[19]. Orange peel, as a readily available natural resource, offers unique
of ethanol. The ethanol in the solution was then evaporated by capillary
advantages. After carbonization, it exhibits distinctive porosity and is
impregnation, leaving a dry substance. After that, 60 mL of distilled
highly self-doped with phosphorus. The introduction of heteroatoms (N,
water was added, the pH was adjusted to 9 and the mixture was stirred

Pyrolysis

Juice factory

Orange fruit Orange peel powder Activated biochar CoNF@OBC

Supercapacitor

Fig. 1. Schematic illustration for preparation of CoNF@OBC composite for application as an electrode material in supercapacitors.

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

vigorously for 3 h to ensure complete dissolution. After placing the GCD graphs were also obtained at various current densities ranging from
mixture in a Teflon tube, it was heated at 120 ◦ C for 10 h. The achieved 1 to 8 A g− 1. The frequency range of the EIS measurement was 105 to
mixture was cooled to room temperature, washed multiple times with DI 0.1 Hz.
water to remove contaminants, and then dried in a hot air oven at 60 ◦ C
for 16 h. In order to create CoNF@OBC-1, CoNF@OBC-2, CoNF@OBC-3, 3. Results and discussion
and CoNF@OBC-4, 2, 4, 8, or 16 wt% Co(OH)2 was added to OBC. The
purpose of this study was to investigate the impact of Co species on the 3.1. Structural and morphological analysis
supercapacitive capabilities of CoNF@OBC nanocomposites.
The XRD patterns of OBC and CoNF@OBC are shown in Fig. 2a. Two
2.3. Characterizations peaks at 25◦ and 42◦ represent the graphite domain (002) and (101)
phases, respectively [21]. Following the decorating of CoNF onto OBC,
The crystallinity of OBC and CoNF@OBC was measured by a Bruker the main diffraction peaks of CoNF@OBC were also noted. The (100),
D8 Advanced X-ray diffractometer (XRD) at λ = 1.5405 Å. The Raman (020), (020), (140), (220), and (300) crystal planes of Co(OH)2 are well
spectra was analyzed to determine via (Bruker Senterra micro-Raman recorded at the peaks at 10.8, 14.8◦ , 17.5◦ , 20.8◦ , 26.7◦ , and 30.4◦
spectrometer). The Fourier transform infrared (FTIR) measurement (JCPDF 00-048-0091). After the loading of CoNF, structural flaws are
was conducted using the KBr method by a (Horiba FT-720 spectropho­ indicated by a decrease in the intensity of the reflection peaks of CoN­
tometer). Specific surface area of the as-prepared CoNF@OBC materials F@OBC [22]. The Raman spectra of OBC and CoNF@OBC with varying
was determined by Micromeritics ASAP 2020 analyzer. The thermal concentrations of CoNF are displayed in Fig. 2b. Specifically, carbona­
stability of the synthesized materials was examined by a thermal ceous materials have peaks in their spectral energy at 1341 and 1590
gravimetric analysis at a heating rate of 10 ◦ C min-1 in N2 gas (TGA, cm− 1, which are referred to as the D and G bands, respectively [23]. The
made by Mettler Toledo). The morphology of the samples was examined G band reflects the sp2 carbon states of the graphitic hexagon-pinch
by a field-emission SEM (Hitachi S-4800) and JEM 2020 transmission mode, while sp3 carbon's first-order scattering produces the D band.
electron microscopes. X-ray photoelectron spectroscopy (XPS) from OBC has a lower ID/IG (0.87) than CoNF@OBC (0.95), which is mostly
Thermo Fisher Escalab Xi+ was used to find out elemental composition explained by cobalt species hydrolyzing carbon [24]. This confirms that
and bonding state with a radiation source at Al 1000 eV. CoNF@OBC can develop more abnormalities and flaws, leading to more
reactive sites for electrochemical reactions. FTIR was used to charac­
2.4. Electrochemical analysis terize surface functional groups of OBC and CoNF@OBC composites.
OBC exhibits a large peak at 2950 cm− 1, which is associated with the OH
A Metrohm Autolab electrochemical station with a three-electrode stretching of alcoholic and phenolic hydroxyl groups, as explores in Fig.
setup was used to test all electrochemical properties (PGSTAT 302N). S1 (Supplementary data). At 1739 cm− 1, the presence of the O– –C group
A homogenous paste was created by thoroughly mixing CoNF@OBC, is demonstrated [25]. Additionally, the biochar's aromatic carbon's C––C
carbon black, and PVDF with the mass ratio 8:1:1 in NMP to provide the stretching is indicated by the peak at 1545 cm− 1. The O–H group can be
working electrode. After the slurry applied across a 1 cm × 1 cm Ni foam identified by the vibrational peak at 3417 cm− 1. Furthermore, the
square, it was then dried for 10 h in vacuum oven at 60 ◦ C. The counter presence of Co3O4 is responsible for the peaks at 612 and 661 cm− 1. The
electrode in the aqueous electrolyte of 1 M KOH was a Pt wire, and the stretching vibration of NO3 that results in the peak at 1399 cm− 1 is
reference electrode was a Hg/HgO electrode. At scan rates between 10 brought on by the Co(NO3)3 residue [26].
and 100 mV s− 1, the voltage for CV testing was set between − 1 and 0 V. Additionally, BET surface area analysis was done on both OBC and

a) (002)
b) D G c) OBC
Adsorbed (cm3 g-1 STP)

CoNF@OBC-1
(020)
Intensity ( a.u )

(001) OBC CoNF@OBC-2

Intensity ( a.u )

(100) CoNF@OBC-3
(020) (140) (220)
(300) CoNF@OBC-1 CoNF@OBC-4
OBC
CoNF@OBC-2
CoNF@OBC-1

CoNF@OBC-3 CoNF@OBC-2
CoNF@OBC-3
CoNF@OBC-4
CoNF@OBC-4
10 20 30 40 50 60 1200 1300 1400 1500 1600 1700 0.0 0.2 0.4 0.6 0.8 1.0
2 (degree) Raman shift ( cm-1) Relative Pressure (P/P0)

d) 100 e)
Mass remaing (%)

90

80

70
CoNF@OBC-4
60
OBC
50
0 200 400 600 800 1000
Temperature (C)

Fig. 2. (a) XRD spectrum of CoNF@OBC with varying Co(OH)2 concentrations, (b) Raman spectrum, (c) N2 adsorption/desorption isotherm and pore size distri­
bution (inset) of CoNF@OBC-4, (d) TGA curves of OBC and CoNF@OBC-4 and (e) Contact angle of water droplet on CoNF@OBC-4 at t = 0 s.

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

CoNF@OBC composites. According to Fig. 2c, OBC demonstrates a detail (Fig. 3). The oval-shaped structure with macropores on the surface
typical type I curve, that denotes the existence of a micropores-rich ar­ of the biochar is visible in the SEM image of OBC (Fig. 3a). The CoNF is
chitecture with a SSA that can exceed 911 m2 g− 1 [27]. The SSA of appropriately placed on the surface of OBC following the hydrolysis of
CoNF@OBC is drastically reduced after Co(OH)2 is deposited. As more Co(OH)2 (Fig. 3b and c). Additionally, the CoNF@OBC-4 TEM pictures
Co(OH)2 is deposited, the surface area of CoNF@OBC nanocomposites show the accumulation of nanosized petals, which results in the devel­
falls drastically. Compared to CoNF@OBC-1 (61 m2 g− 1), CoNF@OBC-2 opment of a flower bloom (Fig. 3d). The high-resolution TEM image,
(23 m2 g− 1), and CoNF@OBC-3 (11 m2 g− 1), the CoNF@OBC-4 has a which has an interplanar spacing of 0.20 nm (Fig. 3e) displays the lattice
significantly small surface area (3 m2 g− 1). As a result, CoNF deposition fringes of the CoNF@OBC-4 crystal plane. Fig. 3f reveals the hexagonal
would result in a smaller SSA. Also, as can be seen in the inset of Fig. S2, lattice structure of the graphite-based materials with sp2 graphite
the mean pore size of CoNF@OBC-4 is 4 nm, making it an ideal material diffraction. Theses findings are highlighed by inversed FFT image
for the transport of electrons and ions during charge-discharge processes (Fig. 3g). In addition, Fig. 3h presents the lattice spacing of 0.173 nm
[7]. TGA was used to look into the thermal behavior of OBC and CoN­ derived from the HRTEM image, corresponding to the d-spacing of the
F@OBC in more detail. As displayed in Fig. 2d, the TGA graph of OBC (1− 100) plane. The functionalized ratios of Co and O are 16 and 32 %,
shows a small loss of weight up to 150 ◦ C, most likely as a result of the respectively, in the OBC support, according to the EDX spectrum in Fig.
moisture evaporation. Moreover, flaws, volatile substances, and the S3 (Supplementary data).
degradation and breakdown of carbon into CO2 and CO cause the mass Further study was conducted in order to evaluate the surface
of OBC to continue to decline after 150 ◦ C [28]. The inclusion of 16 % Co chemical states of OBC and CoNF@OBC-4. Peaks at 285, 406, and 552
(OH)2 helps the composite maintain good thermal stability up to 700 ◦ C. eV are visible in the full scan spectrum of OBC (Fig. 4a), elaborating on
After 700 ◦ C, there is a rapid mass loss that is due to the thermal the presence of C 1s, N 1s, and O 1s. After peak deconvolution, the O1s
breakdown of Co(OH)2 into Co3O4, and the combustion of OBC is peak in Fig. 4b exhibits two distinct features 531.4 eV for Co–O, and
responsible for the latter [29]. As shown in Fig. 2e, a contact angle of 532.3 eV for O–H, respectively.
134.1◦ observed for a water droplet on CoNF@OBC at t = 0 s signifies a The C 1s XPS spectrum (Fig. 4c) reveals three characteristic binding
highly hydrophobic surface. This high angle suggests that the surface is energy peaks for aromatic carbon at 284.1, 286.6, and 289.3 eV, which
very hydrophobic, meaning it repels water. This hydrophobic nature is correspond to C– –C, C–O, and O–C– –O, respectively. The minor
likely attributed to the unique molecular structure and composition of contribution of O–C– –O suggests effective reduction of carbon. These
CoNF@OBC, promoting low surface energy and the presence of hydro­ numbers are in line with earlier findings that have been documented in
phobic moieties. The observable contact angle indicates minimal inter­ the literature [30]. Carbon is being reduced effectively, as evidenced by
action and affinity with water, suggesting a predominantly hydrophobic the extremely little contribution of O–C– –O. The high-resolution XPS
surface. spectra of Co 2p are also obtained (Fig. 4d) These spectra can be further
The morphology of OBC and CoNF@OBC-4 was studied in further deconvoluted into four peaks, two of which are centered at 781 eV and

Fig. 3. SEM of (a) Orange Peel Biochar, (b) and (c) Co(OH)2@OBC-4, (d) TEM images of Co (OH)2@OBC; (e) HRTEM, (f) FFT, (g) inversed FFT, (h) d-spacing of Co
(OH)2@OBC. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

a) OBC b)
CoNF@OBC-4
Co2p

Intensity (a.u.)
Intensity (a.u.)
Co-O
O1s
O-H
C1s

O1s C1s
N1s

1000 800 600 400 200 0 538 536 534 532 530
Binding energy (eV) Binding energy (eV)
c) d) Co 2p3/2
C=C

Intensity (a.u.)
Intensity (a.u.)

Co 2p1/2 Sat
Sat
C-O

O-C=O

290 288 286 284 282 805 800 795 790 785 780 775
Binding energy (eV) Binding energy (eV)
Fig. 4. (a) XRS survey spectrum of OBC and CoNF@OBC-4; (b), (c), and (d) the deconvoluted of core level spectrum for O 1s, C 1s, and Co 2p region of CoNF@OBC-4.

798 eV (red and blue) for Co 2p3/2 and Co 2p1/2, respectively, and two of CoNF@OBC at 100 mV s− 1 with a concentration of 2–16 wt%. The
which are centered at 783 eV and 802 eV (green and yellow), which can CoNF@OBC-4 curves exhibit the biggest area when compared to those of
be regarded as satellite peaks typical of Co The successful preparation of the other CoNF@OBC based materials, demonstrating that cobalt hy­
CoO is supported by such a comprehensive characterisation of the XPS droxide addition can enhance the electrochemical performance and
spectra [31]. capacitance of CoNF@OBC-4 composites. With a rise in the CoNF %, the
area of the CV plots is seen to increase [33].
An electrode's entire capacitance may be split into two equal halves.
3.2. Supercapacitive behavior of electrodes One includes a rapid electrochemical reaction associated with ion
adsorption/desorption (EDLC) and a quick reversible faradaic reaction
A comparison of pure OBC's electrochemical performance was per­ (pseudocapacitance) that is independent of current density or scan rate.
formed first. The OBC CV curves are shown in Fig. 5a at scan rates Ion diffusion to the electrode material is the another process [34]. To
ranging from 10 mV s− 1 to 100 mV s− 1. Scan rates were found to have an accurately describe the charge storage mechanism of electrode material,
unusually rectangular-shaped curve. While scanning at a high pace, the we need to understand which process dominates in the electrochemical
CV curve maintained its quasi-rectangular shape, indicating strong reaction. By dividing the current (I) into capacitive (k1v) effects (elec­
electrochemical reversibility and exceptional capacitive behavior. All trical-double-layer capacitance or redox pseudocapacitance) and
CV curves have a pattern that looks like a rectangle. Low charge transfer diffusion-controlled behavior (k2v1/2), one can determine the both from
resistance can be achieved by using an electrode material with a CV another CV analysis in accordance with the power-law relationship: I =
curve that is rectangular in shape. To learn more about the electro­ k1v + k2v1/2. The analysis from the plot I/v1/2 vs v1/2 directly provides
chemical properties of pure OBC, the GCD of specimens with current k1 and k2 constants at various potentials [35]. CV curve of CoNF@OBC-4
densities ranging from 1 to 8 A g− 1 in a 1 M KOH solution were exam­ is compared with ideal capacitive performance at 10 m V s− 1 in Fig. 5c.
ined. According to Fig. S4 Supplementary data, a triangle-shaped GCD There is no doubt that the low scan rate gives electrolyte ions enough
curve can be seen in all of the GCD curves. Show an IR drop in GCD time to intercalate and diffuse into the electrode channels, explaining
curves that may be caused by internal resistance of ion transport and why the capacitive-controlled reaction only accounts for 29 % of the
electrolyte resistivity. GCD curves also reveal that the specific capaci­ total. The contribution ratio of CoNF@OBC-4 capacitive and diffusional
tances of OBC at 1, 2, 3, 4, and 8 A g− 1 are all in the 290, 206, 165, 152 behavior is displayed as a function of different scan rates in Fig. S6. The
and 110 F g− 1 range. It was found that varying the amount of CoNF capacitive contribution rises up to all curves up to 56 % at 100 scan rate
added to the OBC, from 2 to 16 wt%, improved the electrochemical as the scan rate increases and the CV plot departs from optimum EDLC
performance of the CoNF@OBC composite. With various CoNF ratios, all behavior. At high scan rates, the capacitive behavior of CoNF@OBC-4
of the CV curves of CoNF@OBC exhibit the same quasi-rectangular CV dominates the storage mechanism as evidenced by the rise in
behavior as OBC materials (Fig. S5, Supplementary data). It's interesting capacitive-controlled response at 10 mV s− 1 is 29 %, which further
to note that the CV curves of CoNF@OBC materials exhibit a similar boosts to 56 % at 100 mV s− 1 as shown in Fig. 5d. The intuitive design of
shape with no complete distortion [32]. The limited diffusion channel the representative construction of the CoNF nanoflower anchoring on
for electrolyte ions and the hierarchical structure of the OBC account for the OBC substrate is displayed in Fig. 5e. The CoNF@OBC donates
the majority of this outcome. Fig. 5b compares the CV curves of

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

a) 6 b) 20
4 10

Current (A g-1)
Current (A g-1)
2
0
0
-10
-2
CoNF@OBC-1
-4 -20 CoNF@OBC-2
100 mV/s
70 mV/s CoNF@OBC-3
-6 50 mV/s -30
20 mV/s CoNF@OBC-4
10 mV/s

-8 -40
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs. Hg/HgO) Potential (V vs. Hg/HgO)
c) 6
Scan rate 10 m V s-1 d) 120 Capacitive controlled Diffusion controlled

4 100

Contribution (%)
Diffusion control
Current (A g-1)

2 80

0 60

-2 40

-4 20

-6 0
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 10 20 50 70 100
Potential (V vs. Hg/HgO) Scan rate (mV s-1)
e)

Fig. 5. The CV plots of (a) OBC at scan rate from 10 to 100 mV s− 1 and (b) CoNF@OBC-x at 100 mV s− 1 with a range of Co(OH)2 concentrations of 2–16 wt%, (c)
Capacitive contribution to total charge storage at 10 mV s− 1, (d) contribution ratio of capacitive and diffusion charges against scan rates from 10 to 100 mV s− 1, and
(e) The proposed way for CONF@OBC-4 to store energy for supercapacitance.

another super highway (path 2) for speedier immigration, and its su­ respectively (Fig. 6b). The electrochemical properties of the electrodes
perior electrochemical capabilities can be attributed to conductive OBC and the constructed device were calculated using standard formulate. In
by transporting electrons through the correct channels. Better electrical line with earlier findings, the specific capacitance of CoNF@OBC de­
conductivity, different chemical valence states (Co2+/Co3+), and clines with increasing current density. While CoNF@OBC hybrid open
numerous active sites for reversible redox processes are all provided by channels for rapid electrolyte ion transit to increase surface wettability
CoNF@OBC material, which gives the free-standing electrode a high and electrochemical behavior, OBC acts as a conductive foundation for
pseudo-capacitance [36]. quick electron transfer. Due to the sluggish rate of electrolyte ion
CoNF@OBC-4 composite was also tested for charge-discharge studies diffusion, only a portion of the possible reaction sites in the electrode
to analyze supercapacitive properties (Fig. 6a). The nonlinear curve materials may be exploited. This causes the specific capacitance and
shows that composite materials behave pseudocapacitively in contrast insertion response to degrade significantly at high current densities. An
to pure OBC materials. This is mainly due to the presence of Co(OH)2. It perfect faradaic reaction takes place when the electrolyte ions penetrate
is obvious that CoNF@OBC-4 composite has a remarkable electro­ the CoNF@OBC material because the conductive OBC support can
chemical performance, as the specific capacitances at 1, 2, 3, 4, and 8 A, transport the electrons produced by the CoNF@OBC composite. Because
respectively, 563, 340, 192, 172 to 132 F g− 1 at 1, 2, 3, 4, and 8 A g− 1, of this, CoNF@OBC composites can be used in energy storage devices as

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

Fig. 6. (a) GCD plots for the as-prepared CoNF@OBC-4 electrode, (b) the capacitance of OBC and CoNF@OBC-4 as a result of various current densities, and (c)
cycling stability of prepared CoNF@OBC-4, (d) calculated and measured impedance of CoNF@OBC-4 in the region of 100 kHz to 100 mHz are compared in the
Nyquist plot of CoNF@OBC-4 (inset: the equivalent circuit), (e) Bode plot of impedance vs. frequency, and (f) Bode plot of CoNF@OBC-4 composite.

electroactive materials. like Warburg impedance (W) which shows the resistance to electrolyte
One of the main characteristics to identify the electrode practical ion diffusion, Constant phase element (CPE) which is associated with the
suitability for actual applications is Cyclic stability. CoNF@OBC-4 change in relaxation time, and leakage resistance (RL) which indicates
demonstrates outstanding cycling stability by maintaining 93 % capac­ the leakage of current flow through the double layer at electrode-
itance retention after 10,000 cycles at 1 A g− 1, as shown in Fig. 6c. electrolyte interface. Fig. 6(e) and (f) shows the Bode plots of phase
CoNF@OBC has better cyclability for two reasons. The first less break­ angle vs. frequency and impedance vs. frequency for the same circuit
down of electrode material in an aqueous electrolyte. Another plausible shown in the inset of Fig. 6d. In the low-frequency range, the phase angle
explanation is that the CoNF@OBC composite can improve surface is very close to 45◦ , which shows once again that the CoNF@OBC-4
wettability and electrochemical activity by providing quick and efficient electrode material is a high charge/discharge rate supercapacitor [37].
free pathways for electrolyte ion diffusion [36]. As shown in Fig. 6d, CoNF@OBC composites' data-based specific capacitance is also
CoNF@OBC has a total internal resistance (RS) of about 3 Ω. OBC bio­ compared. Table 1 shows how the chemistry of Co-based compounds on
char shows an RCT value of 16 Ω when 16 wt% Co(OH)2 is added to it nickel foam is different. This study's electroactive supercapacitor prop­
(CoNF@OBC-4), proving that a conductive surface has been created. erty is on par with or even better than that of prior research. The specific
Since electrons move quickly during the charge-discharge cycle, This is capacitance of N-MWCNT nanocomposite produced by Rajendra et al. at
shown by a low Rct value and linearity in the low-frequency range. 0.5 A g− 1 was 225 F g− 1. A specific capacitance of 310 F g− 1 at 0.5 A g− 1
Randle's equivalent circuit model is fitted by employing complex was reported by Bandhana and colleagues. This is just one of several
nonlinear least-squares (CNLS) method to learn more about how the examples of graphene oxides with high specific capacitance, such as N-
impedance discovery is associated with the electrochemical perfor­ FGO, which has been produced by Raouf et al. CoNF@OBC-4 composites
mance. The fitted open circuit from inset Fig. 6d includes parameters (CoNF@OBC-4) have a specific capacitance of 563 F g− 1 at 1 A g− 1 with

7
A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

Table 1 curves in Fig. 7b exhibit good capacitive performance. It to be revital­

Co-based material over Ni foam electrodes in various electrolytes (Table 1). ized that at 1 A g− 1 can produce superior specific capacitance of 124 F
Electrodes Electrolyte Capacitance Current Reference g− 1. The GCD curves for the CoNF@OBC-4 electrode material for current
(F g− 1) density densities ranging from 1 to 8 A g− 1 are shown in Fig. 7c. At various
(A g− 1) current densities, all of the charge/discharge curves exhibit almost
Co3O4@N-MWCNT 3 M KOH 225 0.5 Ag− 1 [5] straight slopes and substantial symmetry. This demonstrates that the
Co3O4 nanosphere 6 M KOH 128 10 mV s− 1 [7] symmetric device capacitive performance is superior. There is a minor
Co-NC3 6 M KOH 310 0.5 Ag− 1 [11] Ohmic drop at a rather under high current density, that is expected to
N-FGO-Co 3 M KCl 512 1 Ag− 1 [14]
rGO@Co3O4/CoO 0.1 KOH 276 5 mV s− 1 [16]
have a significant role in the slower electrochemical kinetics. The spe­
CC-CO3O 1 M KOH 395 5 mV s− 1 [17] cific capacitance of CoNF@OBC-4 is 124 F g− 1 (1 A g− 1) and remains 73
Co3O4/C nanofibers 1 M H2SO4 137 1 Ag− 1 [19] F g− 1 (at 8 A g− 1) as illustrated in Fig. 7d. At high current densities, the
Co3O4-graphene 1 M KOH 319 10 mV s− 1 [22] loss of capacitance is thought to be caused by the IR drop and the fact
Co3O4 NAs 3 M KOH 387 1 Ag− 1 [24]
that nanostructured materials can't take part in electrochemical re­
hydrophilic Co3O4 0.1 Na2SO4 315 5 mV s− 1 [26]
Cobalt oxide/ 1 M KOH 140 20 mV s− 1 [31] actions with electrolyte ions due to short time for interaction [39].
graphene Further analysis was done on the relationship between the power and
CoNF@OBC 1 M KOH 563 1 A g− 1
This work energy densities of CoNF@OBC-4. The produced CoNF@OBC-4 elec­
trode material has good electrochemical performance, as shown by the
Ragone plot in Fig. 7e. The CoNF@OBC-4 has a high power density of
this investigation. In CoNF@OBC, the conductively porous OBC pro­
811–5143 W kg− 1 and a high energy density of 10–41 Wh kg− 1. In
motes surface wettability and electrochemical activity by increasing ion
addition, the electrochemical performance of the CoNF@OBC-4 super­
and electron transport. It also has good electrical conductivity.
capacitor is compared to those previously reported supercapacitors
(Table 2), such as Co2MnO4/Co hydroxide, NiCo2O4/Ni0.85Se/AC,
3.3. Supercapacitive behavior of symmetric supercapacitor Co3O4/graphene, CuO@NiCo2O4, NiCo2O4/MnO2, Co3O4/MnO2.
Moreover, the symmetric cell provides 10,000 charge-discharge cycles
By employing 1 M KOH as the electrolyte, a symmetric super­ of long-term stability at a current density of 1 A g− 1 (Fig. 7f). The
capacitor was put together to investigate the operational application of CoNF@OBC-4 based supercapacitor device has a capacitance retention
the CoNF@OBC composite material. The CV plots of CoNF@OBC-4 at of 92 %, which is greater than the reported figures displayed in Table 2.
various potential windows are shown in Fig. 7a. In a noteworthy po­ As constructed, the symmetric CoNF@OBC device has showed
tential range of 0 to 1.9 V, the symmetric CoNF@OBC can perform well outstanding electrochemical performance in the presence of basic elec­
as a supercapacitor material. The material on the electrodes starts to trolyte with a potential window of 0–1.6 V. In addition, this low-cost
become diffused at potentials higher than 1.6 V. So, the range of po­ green sustainable approach may open the door to industrial-scale use
tentials for more electrochemical measurements is between 0 V and 1.6 of high-performance energy storage devices. A 1.5 V working potential
V [38]. The CV plots for symmetric CoNF@OBC-4 electrode materials at was applied to the symmetric CoNF@OBC device in order to test its
scan rates that range from 5 to 100 mV s− 1 and voltage ranges from 0 to practical usability. As illustrated in Fig. S8 (Supplementary data). The
1.6 V are shown in Fig. 7b. The approximately rectangular-shaped CV supercapacitor device can lightened LED for 34 s after charging at 1 A

a) 15 b) 10 c) 1.8
1 A g-1
1.5 2 A g-1
10 5 3 A g-1
Current (A g-1)
Current (A g-1)
Current (A g-1)

1.2 6 A g-1
5 8 A g-1
0 0.9
0 100 mV s-1
0-1 V 70 mV s-1 0.6
-5 0-1.3 V -5 50 mV s-1
0-1.6 V
0-1.9 V
20 mV s-1 0.3
-10 10 mV s-1
-10 0.0
0.0 0.5 1.0 1.5 2.0 0.0 0.4 0.8 1.2 1.6 0 100 200 300 400
Potential (V) Potential (V) Potential (V)
d) 140 e) f)
Capacitance Retention (%)

100
120
Specific capacitance (F g-1)

80 1.6
100
Potential ( V )

1.2
60
80 0.8

60
40 0.4

0.0
40 20 0 1000 2000 3000 4000
Time ( s )
20 0
0 3 6 9 0 2000 4000 6000 8000 10000
-1
Current density (A g ) Cycle Number
Fig. 7. (a) CV plots of CoNF@OBC-4 at various voltage windows scan rate of 100 mV s− 1, (b) CV plots at scan rates of 10–100 mV s− 1 with functional window of 1.6
V, (c) GCD plots of symmetric device at 1–8 A g− 1, (d) calculated specific capacitance for CoNF@OBC-4 device as a result of current density, (e) Ragone plot
comparison of symmetric CoNF@OBC-4 based devices, and (f) cycling life test at a applied current density of 1 A g− 1.

8
A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

Table 2 4. Conclusions
A performance comparison of our CoNF@OBC device with other CoO-based
devices. In summary, a composite of cobalt hydroxide and biochar made from
Electrodes Electrolytes Energy Power Capacitance Reference orange peel has been synthesis successfully for use in high-performance
density density retention supercapacitors. The manufactured OBC has a hierarchical structure
(%) with the surface carrying oxygen-containing group, which is the perfect
Co2MnO4/Co 2 M KOH 28 571 70 % (3000) [33] hydrophilic carbon-based base to offer adequate paths for the quick
hydroxide movement of electrons and electrolyte ions, resulting in good conduc­
NiCo2O4/ 1 M KOH 29 99 83 % (5000) [36]
tivity and high EDLC capacitance. Additionally, the performance of the
Ni0.85Se//
AC energy storage's electrochemical system is enhanced by the deposition of
Co3O4/ 2 M KOH 2 856 95 % (1000) [31] CoNF, which raised the pseudo-capacitance of CoNF@OBC composite.
graphene The CoNF@OBC-4 electrode material displays an exceptional specific
CuO@NiCo2O4 6 M KOH 28 750 98 % (2000) [37] capacitance of 563 F g− 1 at 1 A g− 1. The CoNF@OBC based assembled
NiCo2O4/ 6 M KOH 23 133 81 % (5000) [38]
MnO2
symmetric supercapacitor on Ni foam exhibited exceptional energy
Co3O4/MnO2 1 M LiOH 18 158 95 % (5000) [36] storage performance as-fabricated. An ultrahigh energy density of 41
Co3O4/CNC 6 M KOH 13 230 96 % (5000) [40] Wh kg− 1 and maximum power density of 811 W kg− 1 at 1 A g− 1 were
NiCo2O4 1 M KOH 22 750 88 % (2000) [37] obtained under the operating voltage range of 0–1.6 V. When the current
nanospheres
density was raised to 8 A g− 1, the energy and power densities could
CoNF@OBC 1 M KOH 41 811 94 % This work
(10,000) remain at 10 Wh kg− 1 and 5143 W kg− 1, respectively. The CoNF@OBC
supercapacitor demonstrated its long-term stability after 10,000 charge-
discharge cycles with 96 % of the initial capacitance still be maintained.
1
g− for 8 s. These results confirm the potential combination of CoNF and OBC to
After 10,000 cycles, the elemental species were characterized using construct a promising electrode material for high-performance energy
XPS analysis. The C 1s (284 eV), O 1s (531 eV), and Co 2p (780 eV) storage devices.
peaks, originally from the composition of CoNF@OBC-4, are shown in
the survey spectrum (Fig. 8a). The three distinctive binding energy CRediT authorship contribution statement
peaks for aromatic carbon at 284.7 and 287.8 correspond to C– –C, C–O,
and O–C– –O, respectively are shown in Fig. 8b, degrading process oc­ Akhil Pradiprao Khedulkar: Conceptualization, Data curation,
curs on the CoNF@OBC-4 surface. After peak deconvolution, the O1s Formal analysis, Investigation, Methodology, Software, Visualization,
peak in Fig. 8c exhibits two distinct features 531.4 eV for Co–O, and Writing – original draft, Writing – review & editing. Wan-Ju Yu: Data
532.3 eV for O–H, respectively. Additionally, Co 2p XPS spectra are curation, Methodology, Writing – review & editing. Van Dien Dang:
obtained (Fig. 8d). The positions of the peaks have not significantly Data curation, Writing – review & editing. Bidhan Pandit: Software,
changed. Two of which are centered at 785 eV and 803 eV (green and Supervision, Validation, Writing – review & editing. Ruey-an Doong:
yellow) for Co 2p3/2 and Co 2p1/2, respectively, and at 780 eV and 798 Funding acquisition, Project administration, Resources, Supervision,
eV (red and blue) for Co 2p3/2 and Co 2p1/2, respectively, showing the Validation, Writing – review & editing.
exclusive presence of Co+2 species after several 10,000 cycles [41]. After
10,000 cycles, the SEM picture of the CoNF@OBC-4 electrode material Declaration of competing interest
was further assessed as shown in Fig. 8f. According to the penetration
electrolyte ions, some degradation cannot be completely restrained, but The authors declare that they have no known competing financial
the initial structure is still present, demonstrating the potent synergistic interests or personal relationships that could have appeared to influence
impact. The exceptionally stable nature of the supercapacitor is due to the work reported in this paper.
exceptional flexibility of this one-of-a-kind nanoflower structure to the
volume contraction and expansion during cycling.

a) b) c)
CoNF@OBC-4 C=C
Co2p
Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)

O1s
C-O O-H Co-O

O-C=O
C1s

1000 800 600 400 200 0 288 287 286 285 284 283 534 532 530 528
Binding energy (eV) Binding energy (eV) Binding energy (eV)
Co 2p3/2
d) f)
Intensity (a.u.)

Co 2p1/2
Sat
Sat

3 µm
810 800 790 780 770
Binding energy (eV)

Fig. 8. (a) XRS survey scan spectra of CoNF@OBC-4; (b), (c), and (d) the deconvoluted O 1s, C 1s, and Co 2p peaks of CoNF@OBC-4 and (f) SEM images of
CoNF@OBC-4 after cyclic stability studies, respectively.

9
A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

Data availability their performance as photosensitizer of mesoporous TiO2 photoelectrodes, Carbon

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A.P. Khedulkar et al. Journal of Energy Storage 81 (2024) 110302

supercapacitors, RSC Adv. 6 (2016) 63905–63914, https://doi.org/10.1039/ Bidhan Pandit is now a Marie Curie CONEX-Plus researcher at
C6RA10033C. Universidad Carlos III de Madrid (UC3M), Madrid, Spain. He
[38] B. Ren, M. Fan, X. Yang, L. Wang, H. Yu, 3D hierarchical structure electrodes of received his Ph.D. degree (2019) in Physics from Visvesvaraya
MnO2 nanosheets decorated on needle-like NiCo2O4 nanocones on Ni foam as a National Institute of Technology (India) and joined as CNRS
cathode material for asymmetric supercapacitors, ChemistrySelect 4 (2019) Postdoctoral Research Fellow at the Institut Charles Gerhardt
5641–5650, https://doi.org/10.1002/slct.201901018. Montpellier (ICGM), Université de Montpellier (France). His
[39] R.R. Palem, G. Shimoga, I. Rabani, C. Bathula, Y.-S. Seo, H.-S. Kim, S.-Y. Kim, S.- previous scientific interests focus on the synthesis of nano­
H. Lee, Ball-milling route to design hierarchical nanohybrid cobalt oxide structures structures and fabrication of flexible devices for supercapacitor
with cellulose nanocrystals interface for supercapacitors, Int. J. Energy Res. 46 applications. His current research focus includes the synthesis
(2022) 8398–8412, https://doi.org/10.1002/er.7744. of cathode materials for lithium, sodium and potassium-ion
[40] K. Xu, J. Yang, J. Hu, Synthesis of hollow NiCo2O4 nanospheres with large specific batteries, as well as the in situ/operando X-ray based charac­
surface area for asymmetric supercapacitors, J. Colloid Interface Sci. 511 (2018) terizations for the understanding of battery mechanisms.
456–462, https://doi.org/10.1016/j.jcis.2017.09.113.
[41] S. Liu, L. Wang, C. Zheng, Q. Chen, M. Feng, Y. Yu, Cost-effective asymmetric
supercapacitors based on nickel cobalt oxide nanoarrays and biowaste-derived
porous carbon electrodes, ACS Sustain. Chem. Eng. 5 (2017) 9903–9913, https://
doi.org/10.1021/acssuschemeng.7b01860. Ruey-An Doong is a chair professor in the Institute of
Analytical and Environmental Sciences, National Tsing Hua
University, Taiwan. He is also the Dean of Tsing Hua Interna­
tional College. His current research interest includes the fabri­
Akhil Pradiprao Khedulkar received his Ph.D. in Biomedical cation of nanomaterials with novel optical and electrochemical
Engineering and Environmental Science at National Tsing Hua properties for biosensing of analytes, environmentally benign
University, Taiwan in 2023 under the supervision of Professor nanotechnology for treatment of contaminants, and porous
Ruey-an Doong. His research focuses on the fabrication of materials for energy storage and conversion. More recently, his
renewable and sustainable devices from high-valued agricul­ research work also focused on the water-energy nexus and
tural waste biochar’s for supercapacitor applications. He is focus on the fabrication of high-valued biochar's from agricul­
currently working as a postdoctoral researcher at the Depart­ tural waste for water and energy application.
ment of Electrophysics, National Yang Ming Chiao Tung Uni­
versity, Hsinchu, Taiwan.

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