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Ultrafast Graphitization and Reduction of Spongy Graphene Oxide

by Low-Energy Electromagnetic Radiation to Boost the Performance
and Stability of Carbon-Based Supercapacitors
Mohsen Saeidi, Minjong Lee, Odongo Francis Ngome Okello, Si-Young Choi, Seung Soo Oh,*
and Abdolreza Simchi*
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ABSTRACT: Interest in carbon nanomaterials for energy storage

systems such as supercapacitors has enormously risen due to their
attractive electrical conductivity, chemical inertness, and charge storage
capacity. The reduction of graphitic oxide is a versatile procedure to
prepare 3D graphene. Despite many green methods, the dynamics
behind ultrafast thermal graphitization have remained elusive. Here, we
demonstrate an effort to understand the graphitization mechanism of
graphitic oxide under ultrafast thermal reduction induced by
electromagnetic radiation and probably via Ar+ cation collisions. The
low photon energy (10.5 μeV) locally removes oxygen functionalities
and restores the π-conjugated structures. A graphitic structure with
low-defect, long-range order, and relatively high electrical conductivity
(8.7 S cm−1) is attained at a short photoinduced time (15 s) and
relatively low power (1000 W) after a hydrothermal reduction at 160 °C for 2 h. We demonstrate that the prepared spongy graphene
structure microwaved for 13 s is an active charge storage material with a specific capacitance of 226.4 F g−1 at 1 A g−1, an ultrahigh
rate capability of 85.1% in the range of 0.2−50 A g−1, and a capacitance stability of 120% after 10,000 cycles at 1 A g−1. The ultrafast
photoreduction of graphitic oxide for the mass production of graphene sponges paves the way for fabricating functional materials by
tailoring oxygenated functional groups for multiple applications.
KEYWORDS: 3D graphene, photoinduced reduction, electromagnetic graphitization, energy storage, ultrafast charging

■ INTRODUCTION
Recently, three-dimensional foam-like graphene macrostruc-
tures, wherein few-layer graphene sheets are interconnected
with each other, have attracted a great deal of attention. Even
though two-dimensional (2D) graphenemonolayer graph-
iteexhibits outstanding electrical and mechanical properties,
to get better results in macroscopic applications, such as energy
storage devices and high-performance sensors, individual
graphene nanosheets should be integrated into complex 3D
macrostructures.1,2 For example, in constructing electro-
chemical double-layer supercapacitors (EDLCs) used as
battery supplements, 3D graphene foams (3D GFs) with an
ultrahigh specific surface area (SSA) and large pore volume can
be superior to monolayer 2D graphene sheets. Therefore, a
great number of electrolyte ions can be easily and rapidly
adsorbed to the 3D GF surfaces, enabling the development of
EDLCs with excellent rate capability and cycle stability but low
charge storage.3 Along with inherent features of graphene, 3D
GFs with a wide range of pore sizes can possess ultrahigh SSAs
and extremely low densities, as well as fast mass and electron
transport properties, thus making them suitable for many other
applications.1
To synthesize 3D GFs in high throughput, there have been
many different studies to date. They can be classified into two
main approaches: first, direct synthesis by chemical vapor
deposition (CVD),1 epitaxial growth (e.g., SiC),4 3D printing,5
laser-scribing,6 and so forth and second, indirect fabrication
through the reduction of graphene oxides (GOs) by chemical,7
thermal,8 hydrothermal,9 and electrochemical10 treatments.
While the direct synthesis approach typically suffers from the
complexity and difficulty of high-cost processes, the GO
reduction techniques are cost-efficient and scalable, so they are
more advantageous in terms of commercialization. For
instance, CVD-grown GFs exhibit excellent electron mobility
Received: September 17, 2021
Accepted: December 17, 2021
Published: December 30, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsaem.1c02893

367 ACS Appl. Energy Mater. 2022, 5, 367−379
ACS Applied Energy Materials
and electrical conductivity owing to the low levels of structural
defects.1 However, the CVD growth demands the use of
sacrificial templates, high-temperature conditions,11 compli-
cated transfer steps which affect graphene properties and
performance, and sample cleaning procedures to remove
unwanted residues deposited during the transfer process.12
Therefore, this direct synthesis is inappropriate for the mass
production of GFs. Furthermore, the thermal annealing of SiC
wafers necessitates strict chamber conditions (high temper-
ature and/or high vacuum), requires expensive substrates, and
makes the in situ patterning of graphene (during growth)
impossible, limiting its applications.12 The hydrothermal and
thermal treatments of GO sponges were further employed to
be used as a Li-ion battery electrode, bringing about a
moderate electrical conductivity (0.054 S cm−1) due to the
poor graphitization of GO nanosheets.13 Many efforts were
made to recover the conducting π states of sp2-bonded carbon
atoms in graphene nanosheets through eliminating oxygen
functionalities by chemical14 or thermal8 reduction (even at
2850 °C15 ). Nonetheless, removing oxygen species is
accompanied by defect formation in the graphene basal
plane, which declines the ballistic transport path length and
increases scattering sites, resulting in poor electronic properties
of the product.16 Recently, Huang et al.17 synthesized a 3D
interconnected tetratomic-doped (O, B, N, and S) porous
composite carbon from biomaterials via two-step processes of
carbonization and acid-washing treatment. The aqueous
symmetric supercapacitor exhibited an excellent volumetric
energy density and power density with exceptional cycle life.
From a commercial viewpoint, Hu et al.18 claimed a simple,
self-assembly approach for the mass production of 3D
graphene by the reduction of GO using arbitrary conductive
materials. However, poor quality, long reduction time, and low
conductivity of products are still critical problems with GO
reduction methods9 that make them realize their commercial
potential.
To achieve high electrical conductivity in reduced GOs
(rGOs), deoxidation and graphitization mechanisms are
inevitable, which result in the restoration of sp2-hybridized
graphitic carbon.19 Nagase et al.20 studied the mechanism of
thermal reduction (dehydroxylation, decarbonylation, and
decarboxylation) of GO by the density functional theory
(DFT) approach. They showed that the oxygen functionalities
attached to the interior aromatic domain in GO can be
effortlessly detached, both kinetically and thermodynamically,
compared to those at the edges of an aromatic domain. Hence,
hydroxyls located at the inner aromatic domains of GO might
dissociate or migrate to the edges of aromatic domains.
Moreover, decarboxylation is kinetically slow at room temper-
ature; therefore, the carbonyl groups of GO might be removed
spontaneously. However, the carboxyl groups might be slowly
reduced at temperatures of 100−150 °C. A high-temperature
(higher than approximately 700 °C) thermal annealing
eliminates hydroxyl (including those at the edges of aromatic
domains) and carboxyl groups from GO. Huang et al.21 also
proposed a geometry-dependent mechanism for the thermal
reduction of solid GO. They found that in possible reactions
between adjacent GO sheets, where the CO molecules are
released, these molecules have adequate time to react with the
functional groups of neighboring sheets to produce CO2.
Recently, Jang et al.19 reported an in situ deoxidation and
graphitization of GO into 2D high-quality rGO, taking
advantage of the Fischer−Tropsch reaction catalyst
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(CuFeO2). They showed a lower loss of carbon during the
deoxidation process, resulting in almost flawless few-layer
graphene sheets with an average domain size and defect
density 4 times larger and 0.1 times lower, respectively, than
those for thermally rGO (TrGO). Moreover, the electrical
resistance of the synthesized rGO was 246 and 8 times lower
than those of TrGO and CVD-grown graphene, respectively.
Furthermore, a rapid heating process employing a direct-
current arc plasma jet system was studied and the
graphitization of diamond successfully occurred. The prefer-
ential growth along the (002) plane of graphite on the external
surface and grain boundaries was confirmed, although sp3 C−
C bonds were not completely eliminated.22 Jin et al.23 also
investigated the graphitization degree of porous graphitic
carbons using disposable chopsticks as a carbon source and
K2C2O4 and Fe(NO3)3 as an activating agent and graphitic
catalyst, respectively, for supercapacitor applications. The
products exhibited a porous structure and high graphitization
degree, which were controllable by tuning the K2C2O4 content
and the carbonization temperature. The supercapacitor
demonstrated a high specific capacitance (231.1 F g−1 at 0.2
A g−1) and excellent cycling stability.
As a highly energy-efficient and rapid GO reduction method,
localized heating by microwave irradiation can be considered,
in which electromagnetic waves strongly interact with specific
molecules for fast thermal energy production.24 Several studies
have demonstrated the elimination of oxygen species from 2D
GOs by microwaving the liquid phase of suspended GO
nanosheets.25 However, the microwave absorption mechanism
in the solid materials with no dipole movement is different
from polar liquid solutions, making direct 2D GO reduction
challenging.26 Even though solid electron-rich carbon materials
can absorb the microwave energy due to their delocalized π-
electrons from the sp2 hybridization of carbon atoms,27 the low
electrical conductivity of GOs causes low adsorption of
microwave irradiations. Hence, it is expected that partially
rGO might be a good absorber of microwave irradiations in the
presence of free electrons. Chhowalla et al.25 succeeded in
producing a high-quality 2D graphene via the microwave
reduction of moderately conductive rGOs, encouraging us to
utilize such an efficient microwave reduction technique in
fabricating high-quality 3D GFs in a high-throughput manner.
In this study, by applying simple, low-cost, two-step
treatments of hydrothermal and microwave heating, we
showcased the synthesis of fully solid-phase GFs initiated
from 3D hierarchical GO assemblies. Using a polyurethane
(PU) sponge, we easily constructed an initial foam-like GO
scaffold without aggregation or stacking of 2D GOs. The
hydrothermal reaction facilitated the formation of microwave-
reactive rGO backbones. The following microwave irradiation
under argon successfully produced highly conductive 3D GFs
by restoring the π-conjugated structures. However, the
assembly of few-layer 2D graphene nanosheets still retained
numerous ion-accessible micro- and mesopores with lots of
active edge planes, all of which are valuable for electrochemical
applications. The microwave reduction mechanism was also
investigated. As microwave conditions, such as power, time,
and temperature, are readily adjustable, we were able to control
the level of oxygen content in the 3D GFs, in which porosity
was also controlled by replicating the sponge template. By
optimizing the oxygen levels of 3D GFs, we successfully
fabricated high-performance EDLCs with an ultrahigh rate
capability (capacitance retention of 85.1% from 0.2 to 50 A
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Scheme 1. Schematic Illustration of the Procedure Used for the MW-GFs
g−1) and excellent cyclability (capacitance retention of 120%
after 10,000 cycles at 1 A g−1).
■ EXPERIMENTAL SECTION
Materials and Chemicals. A commercially available PU sponge
with a bulk density of 23 ± 0.5 mg mL−1 was purchased from a local
market in South Korea. GO (5 mg mL−1, flake size ranging 0.5−5 μm
with at least 60% of single atomic layer thickness) was supplied by
Graphene Supermarket (USA). Absolute ethanol, KOH, carbon black,
and polytetrafluoroethylene (PTFE) were bought from Sigma-Aldrich
(USA) and used without further purification. All the solutions used in
this work were prepared with 18 MΩ cm−1 DI water.
Assembling of GO Nanosheets in 3D Structures. The overall
procedure is schematically depicted in Scheme 1. The PU sponge was
sliced into cuboids with the dimensions of 1 × 1 × 0.25 cm3 as the
templates of GO assembly (Figure S1a). Incidentally, chunks of
arbitrary-shape sponges can be used for various applications. The
sliced sponges were ultrasonically cleaned in ethanol and deionized
(DI) water. The spongy specimens were immersed in an aqueous GO
suspension (5 mg mL−1) and vortexed for 20 min. The GO
nanosheets were wholly wrapped onto their backbones via a strong
electrostatic effect between amine groups of PU and oxygen
functionalities of GO.28 Afterward, the GO sponges were transferred
into a Teflon-lined stainless-steel autoclave for a hydrothermal
treatment at 160 °C for 2 h (Figure S1b). The product was washed
with absolute ethanol and DI water to remove unattached GO from
the sponge, and then, it was put into a freezer at −80 °C for a few
minutes before the lyophilization treatment at −50 °C and 29 mTorr
overnight (denoted as GOF).
After the hydrothermal reaction, the partially rGOFs were placed in
a vial that was filled with argon gas and subsequently microwaved
(2.54 GHz, 1000 W) for 10, 13, and 15 s, which are denoted as
MW(10s)-GF, MW(13s)-GF, and MW(15s)-GF (Figure S1c),
respectively. It is noteworthy that 3D GOFs with various shapes
and sizes required longer microwave reactions due to their bulky and
highly porous structures. Although no heat treatment is necessary
before the microwave irradiation (as GOFs are hydrothermally
reduced), some GOFs were annealed at 800 °C for 4 h under argon
(denoted as TA-GF) for comparison purposes (Figure S1d).
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■ MATERIAL CHARACTERIZATIONS
The morphology and chemical composition of products were
characterized using field-emission scanning electron micros-
copy (FE-SEM, Hitachi S-4800, Japan) at an accelerating
voltage of 20 kV, equipped with an X-ray energy-dispersive
spectrometer (EMAX ENERGY EX-250, Horiba, Japan).
Transmission electron microscopy (TEM) and high-resolution
TEM (HR-TEM) images and selected-area electron diffraction
patterns (SAED) were obtained by scanning TEM (STEM,
JEOL JEM-2100F, Japan) with an image-forming Cs corrector
and an accelerating voltage of 200 kV to investigate the
nanostructure of samples. For sample preparation, microwave-
assisted preparation of GF (MW-GF) and GO were sonicated
in absolute ethanol, and 7 μL of the solutions was added
dropwise onto a carbon-coated copper TEM grid. Powder X-
ray diffraction (XRD) was performed on a Bruker D2
PHASER diffractometer using monochromatic Cu Kα radiation
(λ = 1.5406 Å) at 30 kV and 30 mA. The diffraction patterns
were obtained at a scan rate of 0.02 °/s over an angular range
of 2θ = 5−40°. The SSA of the samples was determined
according to the multipoint data of nitrogen adsorption−
desorption isotherms (at 77 K) collected on a BELSORP-mini
II analyzer. Before adsorption, the samples were outgassed at
300 °C for 24 h. The values of SSA, external surface area, pore
size distribution (PSD), and pore volume were calculated by
Brunauer−Emmett−Teller (BET), t-plot, Barrett−Joyner−
Halenda (BJH), and nonlocalized density functional theory
(NLDFT, calculated by a SAIEUS software, Ver. 3) models.
The chemical bonding nature of C and O was analyzed by X-
ray photoelectron spectroscopy (XPS) using an ESCALAB
250/VG scientific spectrometer (Thermo Fisher, USA). All
spectra were acquired using an Al monochromatized source
(15 kV, 10 mA) with a spot size of 500 μm and a resolution of
0.64 eV. All samples for XPS were deposited onto a carbon-
tape substrate. The UV−vis absorption spectra were recorded
by a SPARK 10M spectrometer (TECAN, Switzerland) with
DI water as the reference. The Raman spectra were measured
using a WITec alpha 300 RS system with an Nd:YAG laser
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ACS Appl. Energy Mater. 2022, 5, 367−379
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operating at 532 nm with a CCD detector. The reported
spectra were an average of six examinations recorded at various
regions of the samples. The ID/IG and I2D/IG ratios were
determined according to the maximum intensities of the
related peaks. Fourier transform infrared (FTIR) spectra were
acquired from an EQUINOX 55 Bruker spectrometer. The
two-probe method was employed for measuring the electrical
conductivity of the samples using a Keithley 4200 semi-
conductor characterization system.
Electrochemical Measurement. The supercapacitor
response of the 3D graphene-based electrodes was evaluated
in a three-electrode configuration. The working electrodes
were designed as a mixture of 90 wt % (about 2 mg) of the
active materials, 5 wt % of PTFE with a few drops of ethanol,
and 5 wt % of carbon black. The prepared paste was then
pressed into a Pt foil (1 × 1 cm2). The electrodes were dried in
a vacuum oven at 80 °C overnight. An Ag/AgCl reference
electrode and a platinum counter electrode were also
employed. The 6.0 M KOH solution was used as the
electrolyte. Although organic electrolytes have the advantage
of broadening the potential operating windows (up to 4 V),
only an aqueous KOH electrolyte was used in this work due to
its cost-effectiveness, longer cycle life, less internal resistivity,
inflammability, and lower hazard level.29 Before electro-
chemical measurements, the active materials were vacuum-
infiltrated by the electrolyte to access electrolyte ions on the
material’s surface.
For electrochemical examinations, a software-controlled
Autolab 302N potentiostat/galvanostat system (Eco-Chemie,
The Netherlands) was employed. Cyclic voltammetry (CV),
galvanostatic charge/discharge (GCD), and electrochemical
impedance spectroscopy (EIS) were carried out to characterize
the electrochemical response of the materials and super-
capacitor devices. EIS was performed in a FRA32M module in
the frequency range of 0.01 Hz−100 kHz with a superimposed
alternating potential of 5 mV amplitude in a single sine mode.
To evaluate the cycle life via the GCD test, a LAND CT2001A
battery tester was employed. A Luggin capillary with a tip fixed
at 1 mm from the working electrode surface was employed to
minimize the IR drop in the electrolytes.
Calculations. All calculations for electrode properties were
conducted according to the procedures reported in other
studies.30 In brief, the specific capacitance of the electrodes was
determined from the corresponding CV curves according to
the following equation
V
∫V c I(V ) dV
Cs = a thousand celsius, microwave treatment for 1−2 s might be long
m ·ν·ΔV (1)
where Cs is the specific capacitance (F g−1), m is the mass of
the electroactive materials in the electrodes (g), and ν is the
potential scan rate (mV s−1). Vc and Va are the integration
limits of the voltammetric curve (V) and I(V) denotes the
response current (A). The specific capacitance from the GCD
curves was calculated by the following equation
I ·Δtd
Cs =
m ·(Vmax − Vmin) (2)
where Cs is the specific capacitance (F g−1), Δtd is the
discharge time (s), m is the mass of electroactive materials in
the electrodes (g), and (Vmax − Vmin) is the potential change
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excluding the equivalent series resistance (ESR) and equivalent
distributed resistance (if applicable).
■ RESULTS AND DISCUSSION
Scheme 1 depicts the overall fabrication procedure for the
microwaved 3D graphene. In short, the PU sponges with a
bulk density of 23 ± 0.5 mg mL−1 (Figure S1a) were sliced
into cuboids with the dimensions of 1 × 1 × 0.25 cm3 as the
templates before immersion into GO solutions (5 mg mL−1).
Afterward, the mixture was vortexed for 20 min and the
hydrothermal treatment at 160 °C for 2 h was conducted
(Figure S1b). Then, the as-prepared GO sponges were washed
with absolute ethanol and DI water and lyophilized at −50 °C
overnight (denoted as GOF with a bulk density of 36 ± 0.5 mg
mL−1). The GOFs were subsequently microwaved at 2.54 GHz
and 1000 W under argon for various durations ranging from 10
to 15 s, denoted as MW(duration time)-GF (Figure S1c).
Although no heat treatment is necessary before the microwave
irradiation (as GOFs are hydrothermally reduced), some
GOFs were annealed at 800 °C for 4 h under argon (denoted
as TA-GF with a bulk density of 13 ± 0.5 mg mL−1) for
comparison purposes (Figure S1d). The microwave procedure
is shown in Video S2.
The characterization of GO is presented in Figures S2a−e
and discussed in the Supporting Information. Table S1
presents and compares the bulk density, relative density, and
porosity of all the samples. The results indicate that after
microwave irradiation, the bulk density of the GOF remarkably
reduced (10.3 ± 0.7, 4.9 ± 0.4, and 4.1 ± 0.5 mg mL−1 for
MW(10s)-GF, MW(13s)-GF, and MW(15s)-GF, respec-
tively), signifying the removal of the PU backbone and oxygen
functionalities. Interestingly, the densities of the materials after
the microwave treatment for 13 and 15 s are similar. These are
much less than the difference between the commercial sponge
and GOF densities (∼13 mg mL−1). This finding affirms that
after 13 s of irradiation, a major elimination of the oxygen
species occurs. Meanwhile, all samples prepared by the
microwave procedure are highly porous (>99.5%). The bulk
density of TA-GF (13 ± 0.8 mg mL−1) is slightly higher than
that of MW(10s)-GF (10.3 ± 0.7 mg mL−1), showing that the
microwave reduction at 1000 W for 10 s under argon might be
more efficient than the thermal reduction at 800 °C for 4 h
under argon.
The electromagnetic wave energy for a photon from the 2.54
GHz microwaves equals 10.5 μeV [E = hν = (4.1357 × 10−15
eV s) × (2.54 × 109 s−1)]. Since microwave arcs typically last
for 50−100 ms and the temperature increases to several
enough for the reduction of 2D GO into graphene.25 However,
3D GOFs with various shapes and sizes require longer
microwave reactions due to their bulky and highly porous
structures. When we observed the arcs in our experiments, the
temperature was measured at about 2670 ± 20 °C. These arcs
signify that the hydrothermal treatment partially reduces the
GO sponge in order to adsorb microwave irradiations. Hence,
the initial hydrothermal reduction is crucial to make a
minimum conductivity in the rGO, which is well in agreement
with Chhowalla et al.’s report.25
The two-step hydrothermal and microwave treatment
successfully produces 3D GFs whose shape perfectly resembles
that of the sponge template. To confirm, the morphology and
chemical composition of the commercial sponge, GOF, TA-
GF, and MW(15s)-GF were examined by an optical micro-
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ACS Applied Energy Materials
scope and EDS-equipped FE-SEM. Figure 1a,b demonstrates
the backbone of PU commercial sponges. After the hydro-
Figure 1. FE-SEM image of (a,b) PU sponge, (c,d) GOF (GO sponge
hydrothermally reduced at 160 °C for 2 h), (e,f) MW(15s)-GF (GOF
after the microwave irradiation at 1000 W for 15 s under argon), and
(g,h) TA-GF (GOF after thermal annealing at 800 °C for 4 h under
argon). TEM micrographs of (i,j) GO and (k,l) MW(15s)-GF. Insets
of (i,k) show the corresponding SAED pattern.
thermal treatment of the GO sponge at 160 °C for 2 h and the
washing step, the interconnected network of the GO-wrapped
sponge is developed (Figure 1c,d), which resembles the replica
structure of the spongy template. As depicted in Figures 1e and
S3a−d, after the microwave treatment of the GOF (a cuboid
sample with the dimensions of 1 × 1 × 0.25 cm3) at 1000 W
for 15 s (MW(15s)-GF), a spongy network of interconnected
graphene sheets is attained. At higher magnifications (Figures
S3b,c, and 1f), some broken walls are observed that can be
attributed to the fast reduction and removal of oxygen
functionalities and rearrangement of the graphene basal
plane.25 Ruoff et al.31 have reported that during microwave
irradiation at 1100 W for 40 s, overlapped and crumpled RGO
sheets are formed. Similar to CVD-grown GFs,1,32 vertically
standing graphene nanoflakes with sharp edges are observed
(Figure 1e). It is noteworthy that thermal annealing at 800 °C
for 4 h does not significantly change the interlinked structure
of the TrGO (TA-GF) (Figure 1d,h).
Figures 1a and S4a,b indicate that the pore size of the
commercial sponge is in the range of 200−500 μm and the
backbone thickness is between 30 and 60 μm. The size of the
pores in MW(15s)-GF ranges from a sub-micrometer to
several micrometers. The magnified FE-SEM images (Figure
S3a−d) show that the walls are hollow, ultrathin, and rough.
The formation of a highly roughened surface in GFs by the
lyophilization of GO sludges has also been reported by Hayes
et al.9 The distorted surface and topography may inhibit face-
to-face restacking of the graphene sheets and boost micropore
and mesopore formations, hinting at the great promise in high-
capacitive graphene-based EDLC electrodes.33
The effect of the hydrothermal temperature, initial GO
concentration, and thermal annealing on the morphology and
microstructure of the samples has additionally been shown and
discussed in Figures S5−S7. To attain a quick overview of the
graphitization and removal of oxygen functionalities due to the
thermal and microwave treatment, EDS was employed. Figure
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S1e−h determines the presence of C, O, and N in the
commercial sponge (Figure S1e); C and O after hydrothermal
(GOF, Figure S1f) and thermal (TA-GF, Figure S1h)
treatments; and C after microwave irradiation (MW(15s)-
GF, Figure S1g). The presence of nitrogen (12.3%) in the
commercial sponge correlates with PU. The initial oxygen
content of GO sheets (34.2%, Figure S2b) is reduced to 30.2
and 20.8% after hydrothermal and thermal treatment,
respectively. Nitrogen is not detectable as the GO sheets
from the walls of the sponge are nitrogen-free. Microwave
irradiation further decreases the oxygen content to almost 0%,
which is not detectable by the EDS technique.
Figure 1i−l shows the structural evolution at different stages
of processing, as examined by STEM. Wrinkled ultrathin GO
sheets are stacked together to form thicker flakes with a lateral
size of several microns (Figure 1i). At higher magnifications, an
amorphous structure with a shaded-ring SAED pattern is
observed (Figure 1j). After the microwave treatment, on the
periphery of the flakes, few-layer graphene sheets are observed
(Figure 1k). The inset of Figure 1k illustrates the hexagonal
spot pattern (SAED pattern) of high-quality graphene
demonstrating the crystallization of amorphous GO into the
hexagonal graphene. In agreement with previous studies,33 the
lattice fringe at the edges of the nanosheets has a few
irregularly stacked layers. At higher magnifications, narrow
belt-like nanoflakes are observed (Figure 1l). The plane
spacing is about 0.35 nm, which is slightly higher than a (002)
plane spacing in the perfect single-crystal graphite (0.345 nm);
therefore, some degrees of oxygen moieties still exist.34 The
discontinued fringes also show that structural defects exist.35
The results indicate that during microwave irradiation, the
carbon atom rearrangement and effective restoration of the π-
conjugated system occur, leading to the graphitization and
formation of the crystal structure.
The graphitization of GO was further studied by XRD.
Figure 2a indicates two characteristic peaks that correspond to
graphitic domains in graphene (002) and the ordered
hexagonal graphitic structure (100).36 The reduction of GO
is accompanied by a shift in the position of the carbon (002)
peak.37 The interlayer spacing of the (002) peak decreases
from 0.727 nm (2θ = 12.2°) for GO to 0.51 nm (2θ = 17.4°),
0.346 nm (2θ = 25.7°), and 0.338 nm (2θ = 26.3°) for GOF,
TA-GF, and MW(15s)-GF, respectively. The d-spacing for
MW(15s)-GF approximately equals that of graphite (0.336
nm). The results affirm that the hydrothermal, thermal, and
microwave reduction techniques partially eliminate the oxygen
moieties of GO, although the reduction level by the combined
hydrothermal and microwave treatment is the highest. This is
consistent with the HR-TEM results. On the other hand, the
broadening of the graphite (002) peak after the reduction
treatment indicates a smaller sheet size of the reduced products
compared to the original GO.38
Raman spectroscopy is a powerful tool to examine the
structure and the intrinsic quality of graphene.26 The Raman
spectra of the examined carbon nanostructures and the ratio of
peak intensities are shown in Figure 2b and Table S2. These
spectra illustrate the diamond (D) band at ∼1340 cm−1
(stimulated by the A1g phonon) attributed to the defects or
edge areas, which generally originate from vacancies, grain
boundaries, and amorphous carbon species.9 The graphitic (G)
band at ∼1580 cm−1 is attributed to the first-order scattering of
the E2g mode, resulting from the in-plane vibration of highly
symmetrical sp2 carbon domains.26 The 2D peak positioned at
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ACS Applied Energy Materials
Figure 2. Characterization of the carbon nanostructures: (a) XRD patterns; (b) Raman spectra; (c) FTIR spectra; (d) XPS survey scan spectra; (e)
XPS C 1s spectra; (f) XPS O 1s spectra; (g) N2 adsorption/desorption isotherms; (h) PSD based on the NLDFT model; and (i) cumulative pore
volume based on the NLDFT model.
∼2700 cm−1 is triggered by the A1′ phonon but is depressed in
a disordered structure.39 The GO, GOF, and TA-GF exhibit a
prominent D-peak and a broad 2D-peak caused by an
extremely disordered graphitic structure and the incorporation
of a large number of oxygen moieties. Conversely, MW(15s)-
GF displays a sharp, well-defined 2D peak associated with a
pronounced increase of the I2D/IG ratio (0.87 compared to
0.07 and 0.15 for GO and GOF, respectively), which is a
typical characteristic of the few-layer graphene.40 Figure 2b
determines that microwave treatment significantly decreases
the intensity of the D band, while a substantial increase in the
intensity of the 2D band is observable. On the other hand, no
considerable reduction in the D band intensity or appearance
of the intensive 2D band in GOF and TA-GF is noticed. The
decline in the ID/IG ratio from 1.11 for GO to 0.98, 0.71, 0.21,
0.1, and 0.02 for GOF, TA-GF, MW(10s)-GF, MW(13s)-GF,
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and MW(15s)-GF (Table S2), respectively, reflects the
effectiveness of the microwave reduction on the structural
rearrangement of GFs. This is in good agreement with the
STEM and XRD results.41
FTIR spectroscopy demonstrates the effect of microwave
irradiation on the effectiveness of the synthesis process for
reducing oxygen functionalities (Figure 2c). The position of
the peaks and their intensities are shown in Table S3. The GO
spectrum demonstrates dominant peaks at 627, 1629, 2087,
and 3482 cm−1. The broad peak centered around 627 cm−1 is
attributed to the O−C−O out-of-plane deformation (δCOO)28
and aromatic C−H deformation (δCH)42 modes of basal
graphene planes. After hydrothermal treatment, this peak
disappears, while two new sharp peaks are observed. The
intensity of these peaks further decreases after thermal and
microwave reduction, and the peaks completely disappear after
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the microwave treatment for 15 s (MW(15s)-GF). The
attribution of the absorption peak near 1648−1540 cm−1 is
controversial. It can be attributed either to the ketonic CO
stretching vibration (νCO
s ) of carbonyl moieties43 or aromatic
CC bending (νsCC) from the skeletal vibrations of
unoxidized graphitic domains.28,43 The actual value for this
vibration is 1716 cm−1, as calculated by Yin et al.44 They have
claimed that by eliminating the oxidative groups close to the
carbonyl groups, the CO vibrational frequency is red-shifted
to around 1638 cm−1 (78 cm−1 lower), confirming that sp2
carbon atoms exist around the carbonyl group. Moreover, the
transformation of the original band at 1629 cm−1 for GO into
two resolved bands near 1640 and 1550 cm−1, which is close to
the OH deformation peak (δOH), demonstrates that this peak
corresponds to the νCC
s skeletal band of aromatic domains in
other samples.45 By the combined hydrothermal and micro-
wave reduction, the peak intensity declines suggesting the
removal of ketonic species and recovery of the sp2 lattice. The
peak at 2087 cm−1 is attributed to gaseous CO2 being absorbed
on the porous wall of GO from the air,43 while the broad peak
centered at 3482 cm−1 is ascribed to O−H stretching vibration
associated with the hydroxyl groups of GO as GO is
deliberated to be hydrophilic.44 For MW(13s)-GF and
MW(15s)-GF, all the aforementioned peaks are relatively
weak or entirely diminished. The new absorption band at 1540
cm−1 is ascribed to the skeletal vibration of the graphene sheets
(aromatic CC stretching).46 Although MW(15s)-GF con-
sists of a large amount of CC bonds, the corresponding peak
is weak because most of the bonds are located in nearly
symmetrical environments that slightly change their dipole
moment.47 These outcomes reveal that GO was effectively
reduced to 3D graphene via the combined hydrothermal and
microwave treatment.
The XPS technique was further employed to identify the
bonding states and surface functionalities of the samples before
and after the combined hydrothermal and microwave treat-
ments. In the wide-scan or survey spectrum (Figure 2d), only
oxygen and carbon are seen. The C 1s spectrum of GO (Figure
2e) is deconvoluted to three prominent peaks located at 283.4,
285.3, and 286.5 eV. The first two peaks with higher intensity
are ascribed to the negatively charged carbon atoms and the
C−OH bonds, respectively. The third peak at 286.5 eV is
ascribed to positively charged carbon atoms (such as C−O
bonds in alcohols or phenols).26 Other tiny peaks between 286
and 289 eV are typically attributed to hydroxyl, carboxyl,
epoxides, and so forth. The intensity of these peaks immensely
declines after the microwave irradiation; confirming the
removal of the oxygen functional groups.26 The C 1s spectrum
for MW(15s)-GF demonstrates a sharp and high-intensity
peak at 284.5 eV, which is characteristic of graphite structures
(sp2 CC).48 The π → π* shake-up satellite peak appears
around 290.5 eV, which is indicative of the aromatic sp2
carbon-based material. 49 Although this peak could be
attributed to the carbonate or CO2,50 it could also be
attributed to π-electrons delocalized in the aromatic network
because GO does not show this peak. The absence of π-
electron delocalization in the carbon lattice of GO is ascribed
to the low level of aromatic sp2 carbon in the lattice layers due
to the high level of oxygenation, causing severe loss of electrical
conductivity.51 As compared to GO, MW(15s)-GF has a
substantially lower amount of oxygen functional groups,
revealing an extensive deoxygenation process.
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When it comes to the O 1s region, the peak for GO can be
deconvoluted in three oxygen species: CO in an aromatic
structure at 531.2 eV, C−O in an aliphatic structure near 532.7
eV, and C−O in aromatic rings (sp2 carbons) around 533.5 eV
(Figure 2f). The asymmetric peak around 532 eV is attributed
to the graphite structure.50 It is worth noting that the intensity
of CO and C(sp2)−O peaks immensely declines after
microwave irradiation, determining that the oxygen-containing
groups are highly removed, and carbon hybridization changes
to sp2. These results along with HR-TEM images and XRD
patterns (Figures 1i−l and 2a, respectively) affirm that high-
quality 3D-GFs are formed. Table S2 indicates that the C and
O contents of GO are 62.7 and 37.3 wt %, respectively.
Calculating the C/O ratio from the area of C 1s and O 1s
peaks26 (Figure 2e) determines that this ratio is substantially
higher for MW(15s)-GF (62.9) than for GO (1.7). The high
C/O ratio of the microwave-treated sample is beneficial to the
electrochemical stability of electrolytes.52 It is worth noting
that H2O in GO may also contribute to the oxygen content of
GO.53 The oxygen content of the combined hydrothermal and
microwave reduction (1.6 wt %) is lower than those of KOH-
activated 3D-graphene at 1000 °C for 8 h (4.8 wt %),48
hydrazine-rGO (11.8 wt %),54 thermally rGO (2.6 wt %),55
and microwave-reduced 2D graphene (5.3 wt %).25
The N 2 adsorption/desorption isotherms, PSD, and
cumulative pore volume (according to the NLDFT model
assuming slit-shape pores for graphite structures such as
activated carbon56) of the prepared materials are presented in
Figure 2g−i. The SSA and porosity data of the materials are
summarized in Table S4. The combination of I and IV(a) type
isotherms with an H4 type hysteresis loop at the middle-high
region [according to the International Union of Pure and
Applied Chemistry (IUPAC) classification] can be observed in
both MW(13s)-GF and MW(15s)-GF, which is a testimony of
the coexistence of macropores and mesopores in these
samples. Additionally, the hysteresis loop shows that the
isotherm curves are parallel to a greater extent due to higher
graphitization.57 These isotherm curves affirm a well-defined
hierarchical porous architecture for these samples. A
combination of type I and II along with the H4 hysteresis
loop is observed in TA-GF and MW(10s)-GF. Although in
these samples, there is no vertical linear region at a low relative
pressure, indicating the presence of micropore fillings, the
amounts of adsorbed N2 for TA-GF and MW(10s)-GF
samples are much higher than for GOF and GO, suggesting
a higher presence of micropores. Moreover, at the middle-high
relative pressure (P/P0 = 0.4−1), a hysteresis loop is seen for
microwave-treated GO and thermally rGO as an indicator of
mesoporous structures (type IV).58 By contrast, no hysteresis
loop exists for GOF and GO. These isotherms show that
microwaved samples hold an outstandingly higher SSA
compared to those of others when analyzed according to the
BET model: 621.2, 684.0, and 607.5 m2 g−1 for MW(10s)-GF,
MW(13s)-GF, and MW(15s)-GF, respectively, versus 468.9,
72.8, and 11.4 m2 g−1 for TA-GF, GOF, and GO, respectively
(Table S4). Besides, the micropore SSA of MW(15s)-MW is
the highest (914.3 m2 g−1), particularly compared to GO with
an SSA of 18.3 m2 g−1. Similarly, the total pore volume based
on the BJH model increases more than 8 times for MW(15s)-
GF compared to that of the pristine GO. From Table S4, it can
be deduced that the micropore surface area and micropore
volume of MW(13s)-GF constitute a substantial portion of its
total surface area and pore volume, respectively. Hence, this
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Figure 3. CV profiles of the electrodes at scan rates of (a) 1, (b) 100, and (c) 1000 mV s−1. GCD profiles of the electrodes at the current densities
of (d) 0.2, (e) 2, and (f) 20 A g−1. (g) Gravimetric capacitances of the electrodes at various current densities. (h) Nyquist plot of the electrodes.
The insets show the high-frequency region and the corresponding equivalent circuit. (i) Bode plot (phase angle vs frequency) of the electrodes. All
electrochemical experiments were performed in a 6.0 M KOH electrolyte with a three-electrode configuration.

sample can exhibit a high charge capacity.59 SEM studies
(Figure 1e) reveal that the microwave treatment does not
significantly affect the shape and appearance of the GF. Since
the surface area and the pore volume have been increased
remarkably, it appears that the interlaced graphene structure is
well retained, while the microwave reduction triggers the
hierarchical porosities, both micropores and mesopores.50
The PSD and the cumulative pore volume calculated from
the NLDFT method cover both micro- and mesopore ranges
(Figure 2h,i), thereby disclosing the overall pore dimensions.
Apart from GO, other samples show a sharp peak in the
mesopore range. MW(13s)-GF and MW(15s)-GF demon-
strate a large share for pores in a broad range from micropores
to macropores with an average pore width of 3.34 and 5.10 nm,
respectively. In contrast, the PSD of other samples is much
narrower in the micro-/mesopore range. The results signify
that microwave irradiation produces numerous mesopores and
macropores in the carbon nanosheets. The appearance of the
hysteresis loop after the microwave irradiation reveals the
374
broadening of the PSD that can enhance the electrochemical
performance by facilitating ion diffusion through the meso-/
macropores.38
Here, it is pertinent to point out that the N2 adsorption/
desorption technique may not provide an accurate value for
the carbon micropores as a result of the quadrupole moment of
the N2 molecule that restricts the accessibility of the gas to
micropores.60 Likewise, both BET and BJH methods suffer
from some limitations in the micropore evaluation. According
to IUPAC recommendation, the BET analysis is not
recommended for microporous carbon anymore because of
overestimation (by 10−40%) of large micropore surfaces (>0.7
nm) caused by more bilayer gas adsorption on the carbon pore
walls. Due to partial monolayer formation, this method also
underestimates the surface area of pores (<0.7 nm).58 The
discrepancy between the theoretical surface area of graphene
(2630 m2 g−1) and our results might correlate with this fact.
Nevertheless, it can still be useful for comparison purposes.
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The electrical conductivity of GOF, TA-GF, and MW(15s)-
GF is measured using the “two-point probe” setup, which
consists of the contact resistanceas it is not possible to
measure the conductivity of porous structures with the “four-
point probe” method. Each sample is measured three times to
obtain an average value. In general, the electrical conductivity
of rGO can reveal both the extent of the reduction and the
restoration of the electronic conjugation state.35 In fact, the
electron mobility determined by the number of oxygen
functionalities and structural defects in the graphene backbone
affects the electrical conductivity.26 The conductivity values for
the samples are presented in Table S5. The conductivity of
MW(15s)-GF (8.7 S cm−1) raises more than 4 orders of
magnitude compared to that of the pristine GO (4.4 × 10−4 S
cm−1). Electrical conductivity is another significant criterion to
evaluate the π-conjugated system restoration in the MW(15s)-
GF structure. The 4 orders of magnitude increase in the
conductivity after microwave reduction denotes substantial
carbon atom rearrangement and effective restoration of the π-
conjugated system stimulated by the deoxygenation.47,48 The
conductivity of TA-GF and GOF is 0.23 and 9.4 × 10−3 S
cm−1, respectively. These data indicate that the microwave
treatment significantly boosts the conductivity of the carbon
nanostructures. Here, we propose that GOFs are partially
reduced after the hydrothermal treatment through the
restoration of the π-conjugated orbitals. Moreover, the
enhanced electrical conductivity facilitates the absorption of
microwave irradiations.25 Although the MW(15s)-GF con-
ductivity is relatively lower than CVD-grown 3D graphene
(∼10 S cm−1, Table S5), probably owing to its more edge
plane sites, it will be shown in the forthcoming section that
these edge defects improve the electrochemical performance
because edge plane sites are the prevalent origin of fast
electron transfer kinetics in graphitic materials.61
To assess the electrochemical performances of the electro-
des, a three-electrode configuration in an aqueous 6.0 M KOH
electrolyte solution was employed. Figure 3a−f shows the CV
and GCD curves of the samples at the scan rates of 1, 100, and
1000 mV s−1 and current densities of 0.2, 2, and 20 A g−1. At
low scan rates or current densities, all the samples demonstrate
the typical curve of an EDLC (Figure 3a,d). At higher scan
rates or current densities (Figure 3b,c,e,f, respectively), GO
and GOF show a large deviation from the rectangular shape
associated with a large Ohmic drop in the GCD curves. The
area under the CV curve is proportional to the capacitance.
The GOF shows significantly higher capacitance over the other
materials at low scan rates (1 mV s−1, Figure 3a), whereas at a
higher scan rate (100 mV s−1, Figure 3b), MW(13s)-GF
exhibits the largest capacitance. Similar results can be observed
in the GCD response (Figure 3d−f), where the gradient of the
slope of discharge curves after the initial decay, which is related
to the IR drop, is lower for GOF and MW(13s)-GF at low and
high current densities, respectively.
Furthermore, the capacitance performance of TA-GF and
MW(10s)-GF is almost similar. It seems that the effect of the
reduction of oxygen functional groups by 10 s microwave
irradiation on the capacitance is almost identical to thermal
reduction at 800 °C for 4 h. The GOF presents the highest
capacitive value of 412.8 F g−1 at the lowest current density
(0.2 A g−1). Nevertheless, there is a noticeable decrease in its
capacitance (92.5 F g−1) at the current density of 2 A g−1 with
a capacitance retention of 22.4%. Similarly, by raising the
current density from 0.2 to 2 A g−1, GO’s capacitance is
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reduced from 241.6 to 35.2 F g−1with a rate performance of
14.6%. Here, the high electrical resistance of GO, resulting
from poor graphitization and the presence of defects and
oxygen functionalities, leads to an enhanced pseudocapacitance
contribution (Figure S8a).62 This behavior is attributed to a
modest mesopore volume and slight conductivity of GO and
GOF, which results in a large ESR.36,62 On the other hand,
MW(13s)-GF and MW(15s)-GF show a relatively stable trend
upon increasing the current density from 0.2 to 50 A g−1 with
an improved capacitance retention of 85.1% (from 248.2 to
211.1 F g−1) and 86.9% (from 185.6 to 161.3 F g−1) in these
samples, respectively. These electrodes manifest an almost
linear tendency from 0.2 to 50 A g−1 with a more solid
capacitive yield and a desirable rate performance (Figure 3g).
These outcomes support the idea that MW(13s)-GF well
graphitizes GO foams without destroying their structure. The
formed micro- and mesopores in the graphene sheets also
result in the highest capacitance at high scan rates and current
densities. The lower capacitance of MW(15s)-GF compared to
that of MW(13s)-GF can be explained by the hydrophobic
nature of MW(15s)-GF due to the almost complete
elimination of oxygen functionalities, preventing aqueous
electrolytes from penetrating pores and wetting the elec-
trode.62 As illustrated in Figure 3c,f, despite the higher scan
rate (1000 mV s−1) and current density (100 A g−1), both
MW(13s)-GF and MW(15s)-GF samples slightly deviate from
the ideal EDCL. The pure supercapacitor behavior with
negligible ESR and higher mesopore volume makes a more
effective ion transport possible.63 In contrast, TA-GF and
MW(10s)-GF show fish-shaped CV curves accompanied with
a relatively high IR drop in the GCD profiles resulting from
their poor electrical conductivity and graphitization degree.
The CV curves at various scan rates (1−1000 mV s−1) and
GCD profiles at different current densities (0.2−20 A g−1) are
depicted in Figure S8. The Coulombic efficiency (CE) and
energy efficiency (EE) of the GO and GOF samples are much
lower (their CE and EE are in the range of ∼55−80 and ∼12−
33%, respectively) than those prepared by microwave
irradiation (with a CE of >97% and EE of >94% for all the
microwaved samples), confirming a well-established operating
voltage window.64 These observations denote a minimum
degradation of electrolyte at the interface of the electrode and
electrolyte due to the better graphitization and higher
conductivity of microwave-treated samples than GO and
GOF.65
The kinetic analyses further confirm the abovementioned
results (Figure S9). The current response at each potential is
due to the combination of two different mechanisms expressed
by the following equation66
k1 + k 2 ν (3)
where k1 is a rate-independent factor (surface capacitive
effects) and k2ν denotes a diffusion-limited factor evaluated by
the scan rate in the CV experiments.66 The details of the
pseudocapacitance contribution are discussed in the Support-
ing Information.
Detailed insight into the electronic/mass transfer process
happening at the surface of the electrodes is discussed based on
EIS studies. Figure 3h,i depicts the Nyquist and Bode plots of
all electrodes over a frequency range of 100 kHz to 10 MHz at
an open-circuit potential in a 6.0 M KOH solution using the
three-electrode configuration. The Nyquist plot of the
electrodes (Figure 3h) exhibits a semicircle in the high-
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frequency region, followed by a straight line in the low-
frequency region. The equivalent circuit model fitted to the
experimental data is shown in the inset of Figure 3h. The total
cell resistance can be acquired by extrapolating the vertical
portion to find its intersection with the real axis.36 The total
resistance of MW(13s)-GF and MW(15s)-GF is 22.47 and
15.25 Ω, respectively, which is much lower than those of GO
and GOF (1404.9 and 712.4 Ω, respectively). This large drop
in the overall resistances principally arises from the shorter
Warburg region and the reduced charge-transfer resistance
(Rct) of the microwaved samples associated with their
hierarchical pore structure and high pore volume that provide
the more effective mass transfer.36
The ESR comprises the ionic resistance of the electrolyte
and the electronic resistance of the electrodes. These
resistances, which are calculated from the first intercept of
the curves with the real axis in the high-frequency region, are
the key factors in determining the charged/discharged rate and
the power density of a supercapacitor.67 The low ESR
determines that the micro-/mesopores facilitate the efficient
access of electrolyte ions to the graphene surface and shorten
the ion diffusion path.67 The ESRs of MW(13s)-GF and
MW(15s)-GF are 0.87 and 0.053 Ω, respectively, which are
lower than those of GO (54.9 Ω) and GOF (38.4 Ω). To
compensate for the nonideal behavior of the electrodes, a
constant-phase element is considered in the equivalent
circuit.68 Rct is associated with the charge-transfer impedance
at the graphene surface, the electrolyte impedance in small
channels connecting the larger pores, and the diffusion
resistance of the electrolyte.68 The semicircle in the high-
medium frequency region reflects Rct,13 which equals 21.6,
15.2, and 12.1 Ω for MW(13s)-GF and MW(15s)-GF, and
graphene networks,13 respectively. The higher Rct value for GO
(1350 Ω) and GOF (674 Ω) demonstrates faster charge
transfer and less internal electrochemical resistance in the
microwaved electrodes. This trend is inconsistent with the
electrical conductivity results (Table S5). On the other hand,
the sloped lines in the low-frequency zone can be assigned to
the ion transport process or the Warburg resistance.67,68 The
Warburg resistance designates the ion diffusion path lengths
and barriers to the ion exchange. Notably, the slope of the
straight line in the low-frequency region is larger than that of
the 45° straight line, representing an EDLC behavior.67,68 A
near vertical and short tail at low frequencies (an ideal EDLC
behavior) for the MW(13s)-GF and MW(15s)-GF samples
implies lower mass diffusion resistance. Hence, a faster ion
transfer process compared to the other samples is expected.
Figure 3i shows the Bode plot (phase angle vs frequency) of
the electrodes. Once more, the phase angle of MW(13s)-GF
and MW(15s)-GF is nearly −90° at the low-frequency region,
which implies an ideal EDLC behavior.36 The relaxation time
constant (1/f 0, where f 0 is the characteristic frequency at a
phase angle of −45°) is calculated to be 224 and 67 ms for
MW(13s)-GF and MW(15s)-GF, respectively. These values
indicate a much faster response time than many other
graphene-based supercapacitors,69 suggesting that the com-
bined hydrothermal/microwave treatment yields a short
relaxation time for ion transport, promoting rate capability
and cyclic stability.
The cyclic stability of the electrodes was evaluated by the
consecutive GCD experiments at 1 A g−1 for 10,000 cycles.
Figure 4a,b shows the FE-SEM images of GOF and MW(13s)-
GF after the cyclability test. The architecture of the GOF is
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Figure 4. Representative FE-SEM images of (a) GOF and (b)
MW(13s)-GF after subjecting to 10,000 cycles. (c) Cyclic specific
capacitance under a constant current density of 1 A g−1.
almost destroyed and delaminated from the current collector,
while the interlaced 3D graphene structure survives. After
10,000 cycles, the capacitive retention of MW(13s)-GF and
MW(15s)-GF increases slightly [119.9 and 123.4%, respec-
tively (Figure 4c)]. The high capacitive retention of MW(15s)-
GF is attributed to the interlaced 3D graphene structure, which
precludes reaggregation and electrical conductivity.48 Although
the life cycle of supercapacitors normally exhibits a stable or
declining trend in the GCD experiments,70 the enhanced life
cycle is ascribed to the hydrophobic nature of graphene that
requires time to get wet by the aqueous electrolyte and be
activated through the successive GCD process (electro-
activation).70 In contrast to the samples treated by microwave,
the capacitive retention of GO and GOF was reduced to 84.5
and 91%, respectively. The cyclability of TA-GF and
MW(10s)-GF is modest (102.2 and 107.9%, respectively).
As compared to previous studies (Table S6), it appears that
MW(13s)-GF demonstrates desirable capacitance, rate capa-
bility, and cyclic stability. The enhanced graphitization degree
could effectively boost electronic/ionic-transport kinetics,
supporting the rate capability and successfully preventing
electrolyte degradation, which results in a long cyclic life.
To sum up, the 3D graphene network is produced via a
combination of hydrothermal and microwave treatments.
Scheme 1 schematically depicts the overall process to prepare
3D GFs from commercial sponges. After microwave reduction,
the polymeric backbone of the sponge is completely pyrolyzed,
and a hollow structure is formed. The attained graphitic
structure exhibits a high electrical conductivity and active
surface area with many edge planes compared to the pristine
GO. In a mechanistic view, the hydrothermal procedure
removes oxygen functionalities of GO to some extent and
facilitates the absorption of microwave irradiation. It is known
that crystallographic disorder and defects in the graphene
skeleton strongly reduce electron mobility.26 Hereafter, the
electrical conductivity of MW(15s)-GF (8.7 S cm−1) is more
than 1 order of magnitude higher than that of the control
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ACS Applied Energy Materials
sample reduced by thermal reduction at 800 °C for 4 h under
argon (TA-GF with 0.23 S cm−1). Therefore, microwave
irradiation leads to a much-enhanced capability in healing the
lattice imperfections of the graphene skeletons compared to
the thermal reduction. Regarding electrochemical reactions,
these defects produce more edge planes with more active
surface area. Moreover, the restoration of conjugated domains
and elimination of oxygen functionalities, as supported by the
HR-TEM, XRD, FTIR, and XPS analyses, make the GFs more
hydrophobic that affects the wetting of the electrolyte surface
with an aqueous electrolyte. Therefore, there is a trade-off
between the complete removal of oxygen functional groups to
attain an enhanced capacitance with a high rate capability and
long life cycles.
■ CONCLUSIONS
By taking advantage of a two-step reduction process consisting
of a hydrothermal and microwave treatment using commercial
sponges and GO, we synthesized highly conductive 3D-GFs,
providing a simple, fast, cost-effective, and scalable approach to
overcome the critical challenge limiting the large-scale
application of graphene. The microwaved samples demon-
strated unique structural properties, such as a hierarchical
micro-/mesoporous structure, high electrical conductivity, and
ultrathin hybrid walls. The superior capacitive performances of
the graphene-based electrodes including high gravimetric
capacitance, outstanding rate capability, and long cycle life
were demonstrated. It was also shown that the degree of
oxygen functionalities and restoration of graphene lattice
imperfections can be tuned through the duration of microwave
radiation. The electrode prepared by hydrothermal treatment
at 160 °C for 2 h exhibited a capacitance of 412.8 F g−1 at a
low current density. However, the rate capability was relatively
low (showing a retention of 22.4% in the current density range
of 0.2−2 A g−1) due to deficient graphitization and aggregation
of GO sheets, providing a low surface area and pore volume. In
contrast, the sample prepared by the two-step reduction
process exhibited a capacitance of 248.2 F g−1 at 0.2 A g−1 with
a rate performance of 85.1% (at current densities of 0.2−50 A
g−1) and a long cycle life with a capacitance retention of
∼120% after 10,000 GCD cycles at 1 A g−1. It was also possible
to operate the supercapacitors at high rates (50 A g−1). Since a
wide variety of commercially available sponges with different
structures are available, it should be feasible to prepare GFs
with structurally designed features to further boost energy
storage performance. Although we showcased the application
of the procedure for supercapacitors, the GFs with tailored
surface functional groups could be used in a broad range of
electrochemical applications such as electrochemical sensing,
photo-electrocatalysis, electrocatalysis, and biomedical devices
and non-electrochemical applications such as gas and water
purification membranes and oil adsorption materials due to the
adjustable hydrophobicity. In our opinion, this simple and
scalable strategy will accelerate the application of graphene in
real-world products.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.1c02893.
Material characterizations of pristine GO; data of bulk
and relative density as well as the porosity of the
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synthesized samples; supplementary optical and electron
microscopy images of samples with the EDS analysis;
theoretical section for calculations related to the Raman
spectroscopy and corresponding XPS data; data for
FTIR spectroscopy, N2 adsorption/desorption, and
electrical conductivity; and results and discussion for
the supercapacitive properties associated with the
comparison table (PDF)
Microwave procedure of GOFs (MP4)
■ AUTHOR INFORMATION
Corresponding Authors
Seung Soo Oh − Department of Materials Science and
Engineering, Pohang University of Science and Technology
(POSTECH), 37673 Pohang, South Korea; orcid.org/
0000-0001-8045-080X; Phone: +82-54-279-2144;
Email: Seungsoo@postech.ac.kr
Abdolreza Simchi − Department of Materials Science and
Engineering, Sharif University of Technology, 14588 89694
Tehran, Iran; orcid.org/0000-0002-9111-2977;
Phone: +98-21-6616 5226; Email: Simchi@sharif.edu
Authors
Mohsen Saeidi − Department of Materials Science and
Engineering, Sharif University of Technology, 14588 89694
Tehran, Iran; Department of Materials Science and
Engineering, Pohang University of Science and Technology
(POSTECH), 37673 Pohang, South Korea; orcid.org/
0000-0001-5430-3339
Minjong Lee − Department of Materials Science and
Engineering, Pohang University of Science and Technology
(POSTECH), 37673 Pohang, South Korea
Odongo Francis Ngome Okello − Department of Materials
Science and Engineering, Pohang University of Science and
Technology (POSTECH), 37673 Pohang, South Korea
Si-Young Choi − Department of Materials Science and
Engineering, Pohang University of Science and Technology
(POSTECH), 37673 Pohang, South Korea; orcid.org/
0000-0003-1648-142X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.1c02893
Author Contributions
M.S., S.S.O., and A.S. conceived the idea. M.S. designed
experiments; performed the characterizations, analyzed the
data, and prepared the manuscript. M.L. contributed in
performing the experiments. O.F.N.O. and S.-Y.C. performed
the HR-TEM experiment and analyzed the results. S.S.O. and
A.S. developed the concept and methodology, supervised the
research, discussed the results, provided resources and
acquisitions, and revised the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to acknowledge the financial support of the
Sharif University of Technology (grant no. QA970816), Iran
National Science Foundation (INSF Grant 95-S-48740),
National Research Foundation of Korea (NRF) grant by the
Ministry of Science and ICT (2021R1A4A1032162), and
Korea Basic Science Institute (National Research Facilities and
https://doi.org/10.1021/acsaem.1c02893
ACS Appl. Energy Mater. 2022, 5, 367−379
ACS Applied Energy Materials
Equipment Center) grant by the Ministry of Education
(2020R1A6C101A202).
■
REFERENCES
(1) Chen, Z.; Ren, W.; Gao, L.; Liu, B.; Pei, S.; Cheng, H.-M. Three-
Dimensional Flexible and Conductive Interconnected Graphene
Networks Grown by Chemical Vapour Deposition. Nat. Mater.
2011, 10, 424−428.
(2) Chen, Z.; Jin, L.; Hao, W.; Ren, W.; Cheng, H.-M. Synthesis and
Applications of Three-Dimensional Graphene Network Structures.
Mater. Today Nano 2019, 5, 100027.
(3) Schutjajew, K.; Yan, R.; Antonietti, M.; Roth, C.; Oschatz, M.
Effects of Carbon Pore Size on the Contribution of Ionic Liquid
Electrolyte Phase Transitions to Energy Storage in Supercapacitors.
Front. Mater 2019, 6, 65.
(4) Fukidome, H.; Ide, T.; Kawai, Y.; Shinohara, T.; Nagamura, N.;
Horiba, K.; Kotsugi, M.; Ohkochi, T.; Kinoshita, T.; Kumighashira,
H.; Oshima, M.; Suemitsu, M. Microscopically-Tuned Band Structure
of Epitaxial Graphene through Interface and Stacking Variations
Using Si Substrate Microfabrication. Sci. Rep. 2014, 4, 5173.
(5) Sha, J.; Li, Y.; Villegas Salvatierra, R.; Wang, T.; Dong, P.; Ji, Y.;
Lee, S.-K.; Zhang, C.; Zhang, J.; Smith, R. H.; Ajayan, P. M.; Lou, J.;
Zhao, N.; Tour, J. M. Three-Dimensional Printed Graphene Foams.
ACS Nano 2017, 11, 6860−6867.
(6) Stanford, M. G.; Yang, K.; Chyan, Y.; Kittrell, C.; Tour, J. M.
Laser-Induced Graphene for Flexible and Embeddable Gas Sensors.
ACS Nano 2019, 13, 3474−3482.
(7) Yang, Y.; Kang, M.; Fang, S.; Wang, M.; He, L.; Zhao, J.; Zhang,
H.; Zhang, Z. Electrochemical Biosensor Based on Three-Dimen-
sional Reduced Graphene Oxide and Polyaniline Nanocomposite for
Selective Detection of Mercury Ions. Sens. Actuators, B 2015, 214,
63−69.
(8) Cheng, Y.; Zhou, S.; Hu, P.; Zhao, G.; Li, Y.; Zhang, X.; Han, W.
Enhanced Mechanical, Thermal, and Electric Properties of Graphene
Aerogels via Supercritical Ethanol Drying and High-Temperature
Thermal Reduction. Sci. Rep. 2017, 7, 1439.
(9) Hayes, W. I.; Joseph, P.; Mughal, M. Z.; Papakonstantinou, P.
Production of Reduced Graphene Oxide via Hydrothermal Reduction
in an Aqueous Sulphuric Acid Suspension and Its Electrochemical
Behaviour. J. Solid State Electrochem. 2014, 19, 361−380.
(10) Raj, M. A.; John, S. A. Fabrication of Electrochemically
Reduced Graphene Oxide Films on Glassy Carbon Electrode by Self-
Assembly Method and Their Electrocatalytic Application. J. Phys.
Chem. C 2013, 117, 4326−4335.
(11) Marchena, M.; Song, Z.; Senaratne, W.; Li, C.; Liu, X.; Baker,
D.; Ferrer, J. C.; Mazumder, P.; Soni, K.; Lee, R.; Pruneri, V. Direct
Growth of 2D and 3D Graphene Nano-Structures over Large Glass
Substrates by Tuning a Sacrificial Cu-Template Layer. 2D Mater
2017, 4, 025088.
(12) Antonelou, A.; Dracopoulos, V.; Yannopoulos, S. N. Laser
Processing of SiC: From Graphene-Coated SiC Particles to 3D
Graphene Froths. Carbon 2015, 85, 176−184.
(13) Li, B.; Yang, S.; Li, S.; Wang, B.; Liu, J. From Commercial
Sponge Toward 3D Graphene − Silicon Networks for Superior
Lithium Storage. Adv. Energy Mater. 2015, 5, 1500289.
(14) Liu, H.; Hu, X.; Guo, H.; Zhao, J.; Li, F.; Zhu, D.; Liu, S. One-
Step Reducing and Dispersing Graphene Oxide: Via Hydroxypropyl
Hydrazine and Its Applications in Cu2+ Removal. Phys. Chem. Chem.
Phys. 2019, 21, 10947−10954.
(15) Xin, G.; Yao, T.; Sun, H.; Scott, S. M.; Shao, D.; Wang, G.;
Lian, J. Highly Thermally Conductive and Mechanically Strong
Graphene Fibers. Science 2015, 349, 1083−1087.
(16) Dreyer, D. R.; Park, S.; Bielawski, C. W.; Ruoff, R. S. The
Chemistry of Graphene Oxide. Chem. Soc. Rev. 2010, 39, 228−240.
(17) Ma, L.; Bi, Z.; Zhang, W.; Zhang, Z.; Xiao, Y.; Niu, H.; Huang,
Y. Synthesis of a Three-Dimensional Interconnected Oxygen-, Boron-,
Nitrogen-, and Phosphorus Tetratomic-Doped Porous Carbon
Network as Electrode Material for the Construction of a Superior
378
www.acsaem.org Article
Flexible Supercapacitor. ACS Appl. Mater. Interfaces 2020, 12, 46170−
46180.
(18) Hu, C.; Zhai, X.; Liu, L.; Zhao, Y.; Jiang, L.; Qu, L.
Spontaneous Reduction and Assembly of Graphene Oxide into
Three-Dimensional Graphene Network on Arbitrary Conductive
Substrates. Sci. Rep. 2013, 3, 2065.
(19) Yoon, J.-C.; Dai, X.; Kang, K.-N.; Hwang, J.; Kwak, M.-J.; Ding,
F.; Jang, J.-H. Graphitization with Suppressed Carbon Loss for High-
Quality Reduced Graphene Oxide. ACS Nano 2021, 15, 11655−
11666.
(20) Gao, X.; Jang, J.; Nagase, S. Hydrazine and Thermal Reduction
of Graphene Oxide: Reaction Mechanisms, Product Structures, and
Reaction Design. J. Phys. Chem. C 2010, 114, 832−842.
(21) Klemeyer, L.; Park, H.; Huang, J. Geometry-Dependent
Thermal Reduction of Graphene Oxide Solid. ACS Mater. Lett.
2021, 3, 511−515.
(22) Yan, X.; Wei, J.; Guo, J.; Hua, C.; Liu, J.; Chen, L.; Hei, L.; Li,
C. Mechanism of Graphitization and Optical Degradation of CVD
Diamond Films by Rapid Heating Treatment. Diam. Relat. Mater.
2017, 73, 39−46.
(23) Zhang, X.; Li, H.; Zhang, K.; Wang, Q.; Qin, B.; Cao, Q.; Jin, L.
e. Strategy for Preparing Porous Graphitic Carbon for Supercapacitor:
Balance on Porous Structure and Graphitization Degree. J. Electro-
chem. Soc. 2018, 165, A2084−A2092.
(24) Wang, Y.; Sun, W.; Li, H. Microwave-Assisted Synthesis of
Graphene Nanocomposites: Recent Developments on Lithium-Ion
Batteries. Rep. Electrochem. 2015, 5, 1−19.
(25) Voiry, D.; Yang, J.; Kupferberg, J.; Fullon, R.; Lee, C.; Jeong, H.
Y.; Shin, H. S.; Chhowalla, M. High-Quality Graphene via Microwave
Reduction of Solution-Exfoliated Graphene Oxide. Science 2016, 353,
1413−1416.
(26) Zhao, N.; Chen-Yu, W.; Wei, Z. D.; Dong-Ping, W.; Zhi-Bin,
Z.; Shi-Li, Z. Liquid-Phase and Solid-Phase Microwave Irradiations
for Reduction of Graphite Oxide. Chin. Phys. B 2014, 23, 128101.
(27) Devi, N.; Kumar, R.; Singh, R. K. Microwave-Assisted
Modification of Graphene and Its Derivatives: Synthesis, Reduction
and Exfoliation. In Graphene Functionalization Strategies: From
Synthesis to Applications; Khan, A., Jawaid, M., Neppolian, B., Asiri,
A. M., Eds.; Springer Nature Singapore Pte Ltd.: Singapore, 2019; pp
279−311.
(28) Vermisoglou, E. C.; Devlin, E.; Giannakopoulou, T.; Romanos,
G.; Boukos, N.; Psycharis, V.; Lei, C.; Lekakou, C.; Petridis, D.;
Trapalis, C. Reduced Graphene Oxide/Iron Carbide Nanocomposites
for Magnetic and Supercapacitor Applications. J. Alloys Compd. 2014,
590, 102−109.
(29) Yu, A.; Chabot, V.; Zhang, J. Components and Materials for
Electrochemical Supercapacitors. Electrochemical Supercapacitors for
Energy Storage and Delivery: Fundamentals and Applications; CRC
Press: Boca Raton, 2013; pp 182−183.
(30) 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.
(31) Kim, T.; Jung, G.; Yoo, S.; Suh, K. S.; Ruoff, R. S. Activated
Graphene-Based Carbons as Supercapacitor Electrodes with Macro-
and Mesopores. ACS Nano 2013, 7, 6899−6905.
(32) Rahmati, R.; Hemmati, A.; Mohammadi, R.; Hatamie, A.;
Tamjid, E.; Simchi, A. Sensitive Voltammetric Detection of Melatonin
in Pharmaceutical Products by Highly Conductive Porous Graphene-
Gold Composites. ACS Sustain. Chem. Eng. 2020, 8, 18224−18236.
(33) Yan, J.; Liu, J.; Fan, Z.; Wei, T.; Zhang, L. High-Performance
Supercapacitor Electrodes Based on Highly Corrugated Graphene
Sheets. Carbon 2012, 50, 2179−2188.
(34) Shang, N. G.; Papakonstantinou, P.; McMullan, M.; Chu, M.;
Stamboulis, A.; Potenza, A.; Dhesi, S. S.; Marchetto, H. Catalyst-Free
Efficient Growth, Orientation and Biosensing Properties of Multilayer
Graphene Nanoflake Films with Sharp Edge Planes. Adv. Funct. Mater.
2008, 18, 3506−3514.
https://doi.org/10.1021/acsaem.1c02893
ACS Appl. Energy Mater. 2022, 5, 367−379
ACS Applied Energy Materials
(35) Zhang, J.; Yang, H.; Shen, G.; Cheng, P.; Zhang, J.; Guo, S.
Reduction of Graphene Oxide via L-Ascorbic Acid. Chem. Commun.
2010, 46, 1112−1114.
(36) Tian, W.; Gao, Q.; Tan, Y.; Li, Z. Unusual Interconnected
Graphitized Carbon Nanosheets as the Electrode of High-Rate Ionic
Liquid-Based Supercapacitor. Carbon 2017, 119, 287−295.
(37) Liao, K.-H.; Mittal, A.; Bose, S.; Leighton, C.; Mkhoyan, K. A.;
Macosko, C. W. Aqueous Only Route toward Graphene from
Graphite Oxide. ACS Nano 2011, 5, 1253−1258.
(38) Lee, J. H.; Park, N.; Kim, B. G.; Jung, D. S.; Im, K.; Hur, J.;
Choi, J. W. Restacking-Inhibited 3D Reduced Graphene Oxide for
High Performance Supercapacitor Electrodes. ACS Nano 2013, 7,
9366−9374.
(39) Trusovas, R.; Ratautas, K.; Račiukaitis, G.; Barkauskas, J.;
Stankevičienė, I.; Niaura, G.; Mažeikienė, R. Reduction of Graphite
Oxide to Graphene with Laser Irradiation. Carbon 2013, 52, 574−
582.
(40) Ferrari, A. C.; Basko, D. M. Raman Spectroscopy as a Versatile
Tool for Studying the Properties of Graphene. Nat. Nanotechnol.
2013, 8, 235−246.
(41) Yang, D.; Velamakanni, A.; Bozoklu, G.; Park, S.; Stoller, M.;
Piner, R. D.; Stankovich, S.; Jung, I.; Field, D. A.; Ventrice, C. A.;
Ruoff, R. S. Chemical Analysis of Graphene Oxide Films after Heat
and Chemical Treatments by X-Ray Photoelectron and Micro-Raman
Spectroscopy. Carbon 2009, 47, 145−152.
(42) Mageed, A. K.; Dayang Radiah, A. B.; Salmiaton, A.; Izhar, S.;
Abdul Razak, M.; Yusoff, H. M.; Yasin, F. M.; Kamarudin, S..
Preparation and Characterization of Nitrogen Doped Reduced
Graphene Oxide Sheet. Int. J. Appl. Chem. 2016, 12, 104−108.
(43) Sudesh; Kumar, N.; Das, S.; Bernhard, C.; Varma, G. D. Effect
of Graphene Oxide Doping on Superconducting Properties of Bulk
MgB2. Supercond. Sci. Technol. 2013, 26, 095008.
(44) Yin, D.; Lu, N.; Li, Z.; Yang, J. A Computational Infrared
Spectroscopic Study of Graphene Oxide. J. Chem. Phys. 2013, 139,
084704.
(45) Szabó, T.; Berkesi, O.; Dékány, I. DRIFT Study of Deuterium-
Exchanged Graphite Oxide. Carbon 2005, 43, 3186−3189.
(46) Zhu, Y.; Murali, S.; Stoller, M. D.; Ganesh, K. J.; Cai, W.;
Ferreira, P. J.; Pirkle, A.; Wallace, R. M.; Cychosz, K. A.; Thommes,
M.; Su, D.; Stach, E. A.; Ruoff, R. S. Carbon-Based Supercapacitors
Produced by Activation of Graphene. Science 2011, 332, 1537−1541.
(47) Gao, W.; Alemany, L. B.; Ci, L.; Ajayan, P. M. New Insights
into the Structure and Reduction of Graphite Oxide. Nat. Chem.
2009, 1, 403−408.
(48) Wang, C.; Li, D.; Zhai, T.; Wang, H.; Sun, Q.; Li, H. Direct
Conversion of Waste Tires into Three-Dimensional Graphene. Energy
Storage Mater. 2019, 23, 499−507.
(49) Fan, X.; Peng, W.; Li, Y.; Li, X.; Wang, S.; Zhang, G.; Zhang, F.
Deoxygenation of Exfoliated Graphite Oxide under Alkaline
Conditions: A Green Route to Graphene Preparation. Adv. Mater.
2008, 20, 4490−4493.
(50) Hontoria-Lucas, C.; López-Peinado, A. J.; López-González, J.
D. D.; Rojas-Cervantes, M. L.; Martín-Aranda, R. M. Study of
Oxygen-Containing Groups in a Series of Graphite Oxides: Physical
and Chemical Characterization. Carbon 1995, 33, 1585−1592.
(51) Mattevi, C.; Eda, G.; Agnoli, S.; Miller, S.; Mkhoyan, K. A.;
Celik, O.; Mastrogiovanni, D.; Granozzi, G.; Garfunkel, E.;
Chhowalla, M. Evolution of Electrical, Chemical, and Structural
Properties of Transparent and Conducting Chemically Derived
Graphene Thin Films. Adv. Funct. Mater. 2009, 19, 2577−2583.
(52) Sevilla, M.; Mokaya, R. Energy Storage Applications of
Activated Carbons: Supercapacitors and Hydrogen Storage. Energy
Environ. Sci. 2014, 7, 1250−1280.
(53) Zhu, Y.; Murali, S.; Stoller, M. D.; Velamakanni, A.; Piner, R.
D.; Ruoff, R. S. Microwave Assisted Exfoliation and Reduction of
Graphite Oxide for Ultracapacitors. Carbon 2010, 48, 2118−2122.
(54) Morimoto, N.; Kubo, T.; Nishina, Y. Tailoring the Oxygen
Content of Graphite and Reduced Graphene Oxide for Specific
Applications. Sci. Rep. 2016, 6, 21715.
379
www.acsaem.org Article
(55) Acik, M.; Lee, G.; Mattevi, C.; Pirkle, A.; Wallace, R. M.;
Chhowalla, M.; Cho, K.; Chabal, Y. The Role of Oxygen during
Thermal Reduction of Graphene Oxide Studied by Infrared
Absorption Spectroscopy. J. Phys. Chem. C 2011, 115, 19761−19781.
(56) Seaton, N. A.; Walton, J. P. R. B.; Quirke, N. A New Analysis
Method for the Determination of the Pore Size Distribution of Porous
Carbons from Nitrogen Adsorption Measurements. Carbon 1989, 27,
853−861.
(57) Li, Z.; Jaroniec, M.; Lee, Y.-J.; Radovic, L. R.; Engineering, G.
High Surface Area Graphitized Carbon with Uniform Mesopores
Synthesised by a Colloidal Imprinting Method. Chem. Commun. 2002,
1346−1347.
(58) Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P.;
Rodriguez-Reinoso, F.; Rouquerol, J.; Sing, K. S. W. Physisorption of
Gases, with Special Reference to the Evaluation of Surface Area and
Pore Size Distribution (IUPAC Technical Report). Pure Appl. Chem.
2015, 87, 1051−1069.
(59) Chmiola, J.; Yushin, G.; Gogotsi, Y.; Portet, C.; Simon, P.;
Taberna, P. L. Anomalous Increase in Carbon Capacitance at Pore
Sizes Less Than 1 Nanometer. Science 2006, 313, 1760−1763.
(60) Wang, S.; Minami, D.; Kaneko, K. Comparative Pore Structure
Analysis of Highly Porous Graphene Monoliths Treated at Different
Temperatures with Adsorption of N2 at 77.4 K and of Ar at 87.3 K
and 77.4 K. Microporous Mesoporous Mater. 2015, 209, 72−78.
(61) Brownson, D. A. C.; Varey, S. A.; Hussain, F.; Haigh, S. J.;
Banks, C. E. Electrochemical Properties of CVD Grown Pristine
Graphene: Monolayer- vs. Quasi-Graphene. Nanoscale 2014, 6,
1607−1621.
(62) Zhang, L.; Shi, G. Preparation of Highly Conductive Graphene
Hydrogels for Fabricating Supercapacitors with High Rate Capability.
J. Phys. Chem. C 2011, 115, 17206−17212.
(63) Cha, W. S.; Talapaneni, S. N.; Kempaiah, D. M.; Joseph, S.;
Lakhi, K. S.; Al-Enizi, A. M.; Park, D.-H.; Vinu, A. Excellent
Supercapacitance Performance of 3-D Mesoporous Carbon with
Large Pores from FDU-12 Prepared Using a Microwave Method. RSC
Adv. 2018, 8, 17017.
(64) Laheäär, A.; Przygocki, P.; Abbas, Q.; Béguin, F. Appropriate
Methods for Evaluating the Efficiency and Capacitive Behavior of
Different Types of Supercapacitors. Electrochem. Commun. 2015, 60,
21−25.
(65) Tian, W.; Gao, Q.; Tan, Y.; Yang, K.; Zhu, L.; Yang, C.; Zhang,
H. Bio-Inspired Beehive-like Hierarchical Nanoporous Carbon
Derived from Bamboo-Based Industrial Byproduct as High Perform-
ance Supercapacitor Electrode Material. J. Mater. Chem. A 2015, 3,
5656−5664.
(66) Wang, J.; Polleux, J.; Lim, J.; Dunn, B. Pseudocapacitive
Contributions to Electrochemical Energy Storage in TiO2 (Anatase)
Nanoparticles. J. Phys. Chem. C 2007, 111, 14925−14931.
(67) Liu, W.-w.; Yan, X.-b.; Lang, J.-w.; Peng, C.; Xue, Q.-j. Flexible
and Conductive Nanocomposite Electrode Based on Graphene Sheets
and Cotton Cloth for Supercapacitor. J. Mater. Chem. 2012, 22,
17245−17253.
(68) Shabangoli, Y.; Rahmanifar, M. S.; Noori, A.; El-Kady, M. F.;
Kaner, R. B.; Mousavi, M. F. Nile Blue Functionalized Graphene
Aerogel as a Pseudocapacitive Negative Electrode Material across the
Full PH Range. ACS Nano 2019, 13, 12567−12576.
(69) Yang, X.; Cheng, C.; Wang, Y.; Qiu, L.; Li, D. Liquid-Mediated
Dense Integration of Graphene Materials for Compact Capacitive
Energy Storage. Science 2013, 341, 534−537.
(70) Ramadoss, A.; Yoon, K.-Y.; Kwak, M.-J.; Kim, S.-I.; Ryu, S.-T.;
Jang, J.-H. Fully Flexible, Lightweight, High Performance All-Solid-
State Supercapacitor Based on 3-Dimensional-Graphene/Graphite-
Paper. J. Power Sources 2017, 337, 159−165.
https://doi.org/10.1021/acsaem.1c02893
ACS Appl. Energy Mater. 2022, 5, 367−379