Chemical Engineering Journal 393 (2020) 124672

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Chemical Engineering Journal

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

Laser-induced and KOH-activated 3D graphene: A flexible activated T

electrode fabricated via direct laser writing for in-plane micro-
supercapacitors
Huilong Liua,b, Yingxi Xiea, , Junbo Liua, Kyoung-sik Moonb, Longsheng Lua, Zhiran Lina,
⁎

Wei Yuana, Caiwei Shenc, Xining Zangd, Liwei Line, Yong Tanga, Ching-Ping Wongb,
⁎

a
School of Mechanical & Automotive Engineering, South China University of Technology, Guangzhou, GD 510640, China
b
School of Materials Science and Engineering, Georgia Institute of Technology, 711 Ferst Drive, Atlanta, GA 30332, USA
c
Department of Mechanical Engineering, University of Massachusetts Dartmouth, 285 Old Westport Road, Dartmouth, MA 02747, USA
d
Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
e
Department of Mechanical Engineering, University of California, Berkeley, CA 94709, USA

HIGHLIGHTS GRAPHICAL ABSTRACT

• Synchronous induction & activation of

porous graphene on flexible substrate
in air.
• The activation mechanism of porous
graphene via direct laser writing is
demonstrated.
• The effects of KOH on morphology,
composition and wettability are stu-
died.
• Medium concentration of KOH can
improve the quality and wettability of
graphene.
• IMSCs provide 10 times higher energy
density than that without activation.

ARTICLE INFO ABSTRACT

Keywords: Laser-induced graphene (LIG) from polymers has aroused considerable attentions for its low cost and high efficiency
Laser-induced and activated graphene fabrication and prospect applications in flexible micro-energy storage devices. However, its electrochemical perfor-
Direct laser writing mance has been constrained by its purity and macropore-dominated structures. Herein, a one-step, facile approach is
KOH activation reported for synchronous induction and activation of 3D porous graphene from KOH-coated polyimide film by direct
Micro-supercapacitors
laser writing in ambient air. To explore the activation mechanism, the effects of two physical forms of KOH (crystal and
Flexible
solution) with various concentrations are investigated. Studies reveal that medium concentrations of KOH are able to
improve the quality, heteroatoms (nitrogen and oxygen) doping and wettability of porous graphene in comparison with
lower KOH. Additionally, high concentrations of KOH contribute to the formation of carbon atomic defects and me-
soporous structures with increased content of nitrogen (4.94%). Benefiting from the improvement of activation, the
laser-induced and activated graphene-based in-plane micro-supercapacitors present an areal capacitance of 32.00 mF/
cm2 (4.27 μWh/cm2), which is about 10 times higher than that without KOH activation. Good cycling stability, ex-
cellent mechanical flexibility, and outstanding modular integration have been accomplished. As such, these high-
performance devices hold enormous potentials for flexible and wearable electronics.

⁎
Corresponding authors.
E-mail addresses: xieyingxi@scut.edu.cn (Y. Xie), cp.wong@mse.gatech.edu (C.-P. Wong).

https://doi.org/10.1016/j.cej.2020.124672
Received 6 December 2019; Received in revised form 28 February 2020; Accepted 4 March 2020
Available online 05 March 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
H. Liu, et al.
1. Introduction
The blooming and commercial success of portable and wearable
flexible electronics has promoted the technologies of highly integrated
and multi-functional systems with flexible, thin, light and on-chip
characteristics, including the micro-energy storage systems with high
energy and power densities [1–5]. As an important member of micro-
energy storage devices, in-plane micro-supercapacitors (IMSCs) not
only possess the advantages of separator-free, thickness-independent
and size-controllable structural design, but also have the performance
advantages of ultrahigh power density, excellent high-frequency re-
sponse and ultralong life span [6–8]. Over the past decades, great ef-
fects have been devoted to preparing electrode materials, especially
carbon-based materials, for high-performance IMSCs, e.g., onion-like
carbon [9], porous graphene [10], activated graphene [2], and reduced
graphene oxide [11].
Currently, many techniques have been employed for patterning
electrodes for carbon-based flexible IMSCs, such as photolithography
[12–14], plasma etching [15,16], inkjet printing [17], and direct laser
writing [18]. Other techniques require complex processing procedures
or high manufacturing cost, while direct laser writing technique is an
efficient, high-resolution, mask-free, and low-cost processing method,
for great potentials in the fabrication of flexible carbon-based IMSCs
[3,19,20]. According to the difference in processing mechanism, direct
laser writing technique can be mainly divided into three types, in-
cluding laser reduction of graphene/graphite oxide [19,21], laser-in-
duced growth of graphene/graphite from solid carbonaceous sources
[10], and laser etching of carbon-based materials [3,22]. Laser-induced
growth of graphene from polymers for IMSCs has been studied in-
tensively since Lin et al. [10] used polyimide (PI) film as a carbon
precursor to generate laser-induced graphene (LIG) by infrared pulsed
CO2 laser. Subsequently, several polymers were employed as carbon
precursor for LIG, such as polyetherimide (PEI) [10], polyether ether
ketone (PEEK) [23,24], lignin [25], phenolic resin [26], and other
polymers containing aromatic repeating units. Owing to the advantages
of good conductivity, electrochemical performance and commercial
availability, LIG induced from PI film has been widely used in various
fields [27]. To enhance the performance of LIG-based IMSCs, various
methods such as heteroatom doping [28,29], and plasma treatment
[30,31] were employed. Different types of lasers were also applied to
obtain different products, such as infrared femtosecond laser [32,33],
blue-violet semiconductor laser [30], and infrared continuous waves
(CW) CO2 laser [34]. However, previous reported LIG-based IMSCs still
suffer from limited electrochemical performance because LIG fabricated
in ambient air is an amorphous carbon-containing macropore-domi-
nated porous graphene with a nature of hydrophobic. Therefore, it is
necessary to improve the quality, microstructure and wettability of LIG
for high performance IMSCs.
Recently, KOH activation of carbon-based materials at a high tem-
perature (~800 °C) has been proved to be highly effective to improve
the specific surface area of various electrodes [35–38]. For example,
Zhu et al. [35] activated the microwave exfoliated graphene oxide with
KOH at 800 °C. The resulting micro-, mesoporous activated graphene
with ultrahigh specific surface area was used as an electrode for high-
performance supercapacitors. Zhou et al. [39] prepared nitrogen-doped
micro-, mesoporous carbons by KOH activation from a nitrogen-en-
riched carbon and controlled the specific capacitance and nitrogen
content of the as-activated carbons. In the conventional methods, ac-
tivation processes are usually prepared by the carbonization of carbon
precursors in a heating system and then activation of as-prepared
samples by KOH at ~800 °C in furnace under the argon atmosphere
[40], which is costly, and time-consuming. This work presents a new
activation process at room temperature and ambient air via a facile,
low-cost, and environmentally friendly setup. The process can generate
considerable micro-, meso- and macropores and carbon atomic defects
in LIG to improve its electrochemical performance. We have proposed,
2
Chemical Engineering Journal 393 (2020) 124672
for the first time, a synchronous induction and activation method in
one-step to efficiently prepare 3D porous graphene on flexible sub-
strates. This method provides a rapid route to enhance the performance
of carbon-based materials for flexible and wearable electronics and has
great potentials for roll-to-roll production.
Herein, we report on a method for synchronous induction & acti-
vation of porous graphene on a flexible substrate in one-step. The laser-
induced and KOH-activated graphene (LIAG) was prepared by direct
laser writing of different concentrations of KOH-coated PI films in
ambient air. The detailed structure and chemical composition of LIAG,
especially the effect of KOH concentrations on its porous micro-
structure, nitrogen content, lattice size and wettability were in-
vestigated. Studies reveal that medium concentrations of KOH are able
to improve the quality, heteroatoms (nitrogen and oxygen) doping and
wettability (hydrophilic or even superhydrophilic) of porous graphene
in comparison with lower KOH. And high concentrations of KOH con-
tribute to the formation of carbon atomic defects and mesoporous
structures with increased content of nitrogen (4.94%). The LIAG-based
in-plane micro-supercapacitors (LIAG-IMSCs) provide a superior areal
capacitance of 32.00 mF/cm2 at a current density of 0.05 mA/cm2.
Their energy densities (4.27 μWh/cm2) are about 10 times higher than
the ones without KOH activation. Additionally, the LIAG-IMSCs have
good cycling stability (~95% capacitance retention after 6000 cycles),
excellent mechanical flexibility (~85% capacitance retention after
10,000 bending cycles), and outstanding modular integration capability
in series and/or in parallel forms.
2. Experimental section
2.1. Fabrication of KOH-coated PI films
A commercially available Kapton PI film with a thickness of 125 μm
(Du Pont-Toray Co. Ltd) was used as the flexible substrate and carbon
precursor. The PI film was first cut into 60 mm in length and 45 mm in
width and bonded to a planar glass substrate. Subsequently, it cleaned
with anhydrous ethanol, rinsed with deionized water, and dried in a
vacuum oven at 50 °C for 15 min. Two physical forms (crystal and
solution) of KOH (85%, Richjoint) were drop-casting on the surface of
the PI films. The KOH crystals were formed by heating on a hot plate in
air at ~90 °C with supersaturated KOH solutions ranging from 5 to
35 μL. The KOH solutions were prepared from 50 μL KOH solution at
different concentrations between 240 and 1020 g/L (supersaturated).
2.2. Preparation and packaging of LIAG-IMSCs
The fabrication of electrodes for LIAG-IMSCs involves two steps.
First, a CW CO2 laser (10.6 μm) cutting machine (XB4060, Xinbang
Laser Equipment Co., Ltd, China) with ~150 μm beam diameter was
used to write the KOH-coated PI films. Underneath the glass substrate, a
pre-heated steel block with a high specific heat capacity was employed
to prevent the deliquescence of KOH. A laser power meter (VLP-2000,
Beijing Ranbond Technology Co., Ltd, China) was used to measure the
actual mean power of the laser which was set ~1.85 W. Considering the
processing efficiency and activation effect, the scanning speed and dots
per inch (DPI) were optimized and fixed at 30 mm/s, and 1000, re-
spectively. All experiments were performed at room temperature
(25 °C) and ambient air. Afterward, the as-prepared samples were im-
mersed in dilute phosphoric acid (H3PO4, volume fraction 11.1%) and
warm deionized water (50 °C) several times, and dried in a vacuum
oven at 50 °C for 15 min. After drying, the interdigital electrodes were
assembled into LIAG-IMSC devices, where the electrodes served as both
active electrodes and current collectors. Conductive silver paste was
applied to provide better electrical contact between the electrodes and
copper foil. To protect the contact pads from the electrolyte, Kapton PI
tape was used to define the effective interdigitated area of devices.
PVA/H3PO4 ionogel electrolyte was prepared by mixing Poly(vinyl
H. Liu, et al. Chemical Engineering Journal 393 (2020) 124672

alcohol) (PVA, AH-26, SCR) with deionized water and H3PO4 (85%,
Guangzhou Chemical Reagent Factory) (1 g PVA/10 mL H2O/1 g
H3PO4) in 85 °C for about 1 h. Finally, ~0.20 mL of ionogel electrolyte
was drop-casted onto the active electrode area and placed overnight in
a thermostatic desiccator (25 °C) to remove excessive water.
2.3. Materials characterization and electrochemical measurements
Scanning electron microscope (SEM) images and energy dispersive
spectrometer (EDS) elemental mapping were taken on a field emission
scanning electron microscope (Hitachi S4800, 2 kV, Japan). The N2
adsorption/desorption isotherms were tested on a Micromeritics ASAP
2460 analyzer at 77 K for P/P0 of 0.01–0.99. The standard Brunauer-
Emmett-Teller (BET) equation was employed for the calculation of BET
surface area in the range of 0.01 to 0.05 (P/P0), and the original density
functional theory (DFT) model was used to determine the pore-size
distribution. Prior to measurement, each sample was evacuated at
120 °C for 6 h. The sheet resistance was measured using a four-point
probe measurement system (2000 multimeter, Keithley). The thickness
of samples was measured by cross-sectional optical microscope (VH-
Z100R, Keyence Corp., Japan). The wettability was evaluated using a
static contact angle on a JC2000D1 contact angle instrument (CA-D
type, China). X-ray photoelectron spectroscopy (XPS) analysis was
performed on Kratos Axis Ultra-DLD XPS system. X-ray diffraction
(XRD) spectrometry was conducted on a Bruker polycrystall X-raydif-
fraction (D8 Advance) with Cu Kα radiation (λ = 1.5406 Å). Raman
spectra were measured on a micro-Raman spectrometer (LabRAM
Aramis, France) using 532 nm laser excitation. The LIG/LIAG samples
used in the XRD and BET experiments were powder scratched from LIG/
LIAG films.

Fig. 1. Fabrication and characterization of LIAG-IMSC devices. (a) Schematic diagram of the fabrication and (b) corresponding photographs of devices by laser direct
writing on KOH-coated PI film. (c) Optical photographs of typical LIG, LIAG/KC, and LIAG/KS samples before removal of unreacted KOH. (d–h) Top-view SEM
images of LIG, LIAG/KC-35 and LIAG/KS-1020 with magnified images inset, respectively. It can be seen in (g and h) that there are many meso-, macropores on the
walls of graphene. (i and j) Cross-sectional SEM images of LIG, LIAG/KS with magnified images inset, respectively.

3
H. Liu, et al.
The crystalline size along the a axis (La) was calculated from the
intensity ratio of the G peak and D peak in Raman spectra data by the
following equation [41]:
1
10) 4 ID
La = (2.4 × 10 × l ×
IG
where λl is the laser wavelength for Raman measurements.
Cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and
electrochemical impedance spectra (EIS) measurements of IMSCs were
performed using an electrochemical workstation (PGSTAT302N,
Autolab, Switzerland). The EIS of IMSCs were recorded at open circuit
voltage with an AC amplitude of 5 mV in the frequency ranging from
100 kHz to 0.01 Hz. All measurements were tested under ambient
conditions.
3. Results and discussion
The schematic diagram and photographs of the fabrication of LIAG-
IMSC devices are shown in Fig. 1a-c. First, a flexible PI film was coated
with KOH crystal (KC) or solution (KS) by the drop-casting scheme.
After that, a CW 10.6 μm CO2 laser was used for direct writing on the
KOH-coated PI film to prepare LIAG/KC or LIAG/KS. Fig. 1c shows the
optical photographs of partial LIG, LIAG/KC, and LIAG/KS electrodes
Fig. 2. Characterization of LIG, LIAG/KC-15 and LIAG/KS-560. (a) Pore-size distribution and (b) Raman spectra of LIAG/KS-560. (c) XRD patterns of LIG, LIAG/KC-
15 and LIAG/KS-560. (d) XPS survey, (e) C 1s spectra and (f) N 1s spectra of LIG, LIAG/KC-15 and LIAG/KS-560. (g) Schematic structures of PI and LIAG, indicating
the locations of nitrogen and oxygen-containing functional groups.
4
Chemical Engineering Journal 393 (2020) 124672
with different colors, respectively. It can be seen the activation process
enable deepen the color of the electrodes. Then, unreacted KOH was
removed and PVA/H3PO4 hydrogel electrolyte was drop-casted onto the
electrodes to complete the fabrication. By designing the patterns and
controlling the laser scan rate, it is feasible to produce various sizes of
LIAG-IMSCs in a large scale.
It is worth noting that the one-step fabrication of LIAG on a flexible
substrate goes through two stages, that is the formation and activation
of LIG by laser beams. As shown in Fig. S1a, when a PI film is directly
irradiated by a CW CO2 laser beam in ambient air, its surface will suffer
from a rapid high heat load with a local temperature up to 2000 °C in
the interaction region owing to the photothermal effect. PI film can
effectively absorb the incident photon energy provided by the laser
beams at the wavelength of 10.6 μm, leading to internal atomic ex-
citation and generation of carbonized steam [42]. Some excited atoms
are recombined and released as gases in two temperature stages: an
abrupt release of O2, CO and CO2 at a temperature of 550–650 °C and a
gradual release of CH4, H2 and N2 at a temperature above 700 °C [43].
The remaining product is known as LIG with 3D porous structures [10].
After coating a layer of KOH, laser beam can penetrate KOH to induce
the PI into LIG first, and then it enables mix KOH with the as-produced
LIG at the same time. Due to the laser scanning step interval (~50 μm)
less than the laser spot diameter (~150 μm), the LIG/KOH mixtures will
suffer from subsequent three consecutive overlap scans by the laser
H. Liu, et al.
beams (Fig. S1b,c). In the overlap scanning process, the laser acts as a
laser fluence-dependent heating source to selectively provide local
temperature ranging from 500 to 2500 °C [44] to the LIG/KOH mixture
[45]. As reported that KOH will react with carbon-based material under
flowing argon at ~800 °C and the interaction is expressed as:
6KOH + C 2K + 3H2 + 2 K2 CO3 [35]. The difference in this
work is that the experiment was conducted in ambient air, so the re-
sulting product will further react with oxygen. Since the maximum
temperature in PI film up to 1200 °C during processing [44,45], K2CO3
decomposes at the high temperature (> 900 °C) [46] and the reaction
formula can be expressed as: K 2 CO3 K2 O + CO2 (> 900 °C). As
such, it is suggested that the reaction formula of KOH interacting with
carbon-based materials in ambient air at over 900 °C is expressed as:
2KOH + C + O2 K2 O + CO2 + H2 O (> 900 °C). Therefore, the
LIG/KOH mixture will react with oxygen and produce gas after laser
overlap scanning. According to the differences in physical form and the
amount/concentration of KOH, we labeled LIAG/KC-X and LIAG/KS-Y
in this work (where X represents the amount of supersaturated KOH,
and Y represents the concentration of KOH solution).
The surface morphologies of LIG and LIAG are characterized by
scanning electron microscope (SEM). The rapid release of gaseous
products (Fig. 1d) results in an open, interconnected macropore struc-
ture of LIG [47,48]. From the top-view SEM images of LIAG (Fig. S2)
prepared with an increased KOH, we can observe that the structure of
LIG turns from flake foam-like macropore-dominated structure into
bulk macroporous structure at low amount/concentration of KOH (5 μL
or 240 g/L). As KOH further increase (≥15 μL or 560 g/L), the number
of pores on LIAG gradually increases accompanied by decreasing sizes.
As a result, the LIG was turned into the LIAG (Fig. 1e–h) with significant
meso-, macropores appeared on its wall after being activated by KOH,
especially at high amount/concentration of KOH. The energy dispersive
spectrometer (EDS) results in Fig. S3 suggest that the elements of
carbon, oxygen, and nitrogen are evenly distributed within the LIAG
and the content of oxygen and nitrogen increase after activation, which
may be attributed to carbon consumption and oxygen participation
during activation. As shown in Fig. 1i,j, the cross-sectional SEM images
of LIG and LIAG/KS reveal that LIAG has more uniform and smaller size
hierarchical porous structure and thicker section than LIG, suggesting
larger capacity for ions after activation.
To analyze the specific surface area and pore-size distribution of
LIAG, LIAG/KS-560 was studied using N2 adsorption-desorption mea-
surement and LIG was also tested as a comparison. As shown in Fig.
S4a,b, open loops of the adsorption/desorption isotherms for both LIG
and LIAG/KS-560 can be observed at low relative pressure (P/P0). The
open loops belong to the mesoporous hysteresis loops that are caused
by capillary condensation which causes nitrogen molecules to condense
and fill mesoporous channels at below normal pressure. Since capillary
condensation occurs on the liquid surface of the annular adsorption
membrane on the pore wall, the desorption starts from the spherical
meniscus of the pore, so the adsorption and desorption isotherms do not
coincide, forming a hysteresis loop. According to the loop profiles,
LIAG/KS-560 shows a characteristic type-H4 hysteresis loop, while LIG
is type-H3 isotherm character, demonstrating the existence of micro-,
meso- and macropores. The appearance of micro- and mesopores is due
to that the type-H4 isotherm is usually attributed to narrow slit-like
pores, which are characterized by micro- and mesopores, while the
type-H3 isotherm is slit-shaped pores without significant micropores
[49]. This conclusion can also be verified from the difference of LIAG/
KS-560 and LIG in volume absorption under a low P/P0 of 0.1 (Fig.
S4a,b), because nitrogen molecules first diffuse into micropores under
extremely low pressure. In the extremely low P/P0 (below 0.02), the
nitrogen adsorption content of LIAG/KS-560 is about twice higher than
that of LIG, which suggests that LIAG/KS-560 is rich in micropores
instead of mesopores in comparison of LIG [49]. These results show the
coexistence of micro-, meso- and macropores both in LIAG and LIG,
while micropores is richer in LIAG. The Brunauer-Emmett-Teller (BET)
5
Chemical Engineering Journal 393 (2020) 124672
analysis indicates that the specific surface area of LIAG/KS-560 reaches
up to 267 m2/g, which is about twice higher than that of LIG (137 m2/
g), confirming the contribution of KOH activation to the surface area.
Additionally, although LIAG/KS-560 has a larger specific surface area,
it has lower pore volume and average pore diameter than LIG, in-
dicating the pore-size distribution mainly depends on the microporous
structure of LIAG/KS-560 [50]. The pore-size distribution of LIAG/KS-
560 estimated using density functional theory (DFT) mode in Fig. 2a
confirms the presence of micro-, mesopores with diameter located at 8,
12, 16 and 27 Å, respectively. Moreover, compared with LIG in Fig. S4c,
the appearance of smaller pore diameter (8 Å) after activation further
verifies the contribution of KOH activation to micropore content.
Raman spectroscopy, X-ray diffraction (XRD) and X-ray photoelec-
tron spectroscopy (XPS) were used to characterize the chemical struc-
ture and composition of LIG and LIAG. The Raman spectra of LIAG/KS-
560 (Fig. 2b) shows three distinct peaks: D peak at ~1346 cm−1, G
peak at ~1586 cm−1 and 2D peak at ~2685 cm−1. The presence of D
peaks suggests the defective nature of LIG and LIAG, which results from
the distorted sp2-carbon networks [51]. The intensity ratio of D peak to
G peak (ID/IG) was employed to quantitatively assess the crystalline
quality of materials. A high ID/IG indicates the formation of high degree
of crystal plane defects and crystal structure distortion [52]. The XRD
patterns of LIG, LIAG/KC-15 and LIAG/KS-560 in Fig. 2c present an
intense (0 0 2) peak centered at 2θ = 24.68°, 24.24° and 23.92° cor-
responding to an interlayer spacing (Ic) of ~3.60 Å, ~3.67 Å and ~3.72
Å between (0 0 2) lattice planes, respectively. The increased interlayer
spacing suggests the introduction of heteroatom (nitrogen and oxygen)-
containing functional groups in LIG after activation. The presence of a
small shoulder peak nearby ~28° for LIG demonstrates the existence of
a miscellaneous peak, which is the characteristic peak of amorphous
carbon [25]. The disappear of miscellaneous peak for LIAG/KC-15 and
LIAG/KS-560 indicates the decrease of amorphous carbon, which may
be attributed to the fact that amorphous carbon reacts with KOH more
readily than graphene. In addition, compared with LIG, the (0 0 2)
peaks of LIAG/KC-15 and LIAG/KS-560 have reduced intensities and
are slightly broadened due to the formation of micro/mesoporous
structure, which is consistent with the activation results of microwave-
exfoliated graphene oxide [35]. The XPS surveys of LIAG/KC-15 and
LIAG/KS-560 in Fig. 2d show the principal spectra with C 1s peak at
284.5 eV, O 1s peak at 532.3 eV and N 1s peak at 399.0 eV. The C 1s
peak (Fig. 2e and Fig. S5) can be decomposed into three components:
sp2 CeC, CeO & CeN and OeC]O bonding located around
284.45 ± 0.1, 285.40 ± 0.1 and 288.32 eV, respectively [53,54]. It
can be seen that LIAG are dominated by sp2 CeC, consistent with the
results of Raman spectra and XRD pattern. From the water contact
angles in Fig. S6a, we can observe that the hydrophobic LIG (102.96°)
turns into hydrophilic (43.32° for LIAG/KC-15) or even super-hydro-
philic (7.77° for LIAG/KS-560) after activation, which is mainly due to
the increased oxygen-containing groups (Fig. S6b), especially carboxyl
and hydroxyl groups, and the formation of hierarchical porous struc-
tures. In Fig. 2f, the N 1s peak can be deconvoluted into four subpeaks:
pyridinic N, pyrrolic N, quaternary N and N-oxide bonding centered at
398.40, 399.92, 401.10, and 402.80 eV, respectively. It suggests that
pyrrolic and pyridinic N dominate in LIG/LIAG, which is consistent
with theoretical prediction that N atoms have more thermodynamically
stable at the edges of graphene lattice [55]. Fig. 2g shows the schematic
mechanism for the preparation of LIAG from PI with the laser photo-
thermal effect and KOH activation mechanism. As can be seen, the re-
sulting LIAG has considerable defects, doped nitrogen, and oxygen-
containing functional groups.
To investigate the effect of KOH activation on the chemical structure
of porous graphene, Raman spectrum and XPS of LIAG were char-
acterized. Fig. 3a,b shows the Raman spectra of LIAG that are prepared
using KC ranging from 5 to 35 μL or KS at the concentrations between
240 and 1020 g/L. When KOH increases from 0 to 5 μL or 0 to 240 g/L
or below, a broad D peak, narrow G peak and a weak 2D peak can be
H. Liu, et al. Chemical Engineering Journal 393 (2020) 124672

observed, which indicates the formation of low-graphitic carbon at low
amount/concentration of KOH. As KOH increases to 15 μL or 560 g/L, a
narrow and weak D peak and an enhancement of G and 2D peaks were
achieved, suggesting the formation of higher quality graphene structure
[25], and confirming that amorphous carbon reacts with KOH more
easily than porous graphene at this amount/concentration. However, a
wide D peak and a shrinkage of G and 2D peaks were obtained with
further increase of KOH amounts/concentrations. The Raman spectra
were further analyzed and summarized in Fig. 3c,d. As shown, LIAG/
KC-15 and LIAG/KS-560 have the lowest ID/IG ratio, indicating the
maximized crystalline size along the a axis (La) of graphene were ob-
tained at 15 μL or 560 g/L (Fig. 3e) owing to the maximum reduction of
amorphous carbon. Additionally, with the increase of KOH from 0 to
5 μL or 0 to 240 g/L, the I2D/IG ratio drops to a minimum value due to
the formation of low-graphitic carbon, and then it reaches a maximum
value when KOH increases to 15 μL or 560 g/L, demonstrating the
stacking of fewest-layered graphene [56]. The full width at half max-
imum (FWHM) of G peak reach maximum at 15 μL or 560 g/L, which
may be the result of high content of heteroatom (nitrogen and oxygen)
doping in graphene (Fig. S7) [57]. Therefore, in the case of low and
medium KOH, analysis indicates that increasing the amount/con-
centration of KOH can improve the quality and heteroatom (nitrogen
and oxygen) doping of porous LIAG. However, when KOH reaches
higher (≥35 μL or 1020 g/L), porous graphene is overactivated and
considerable number of atomic defects are produced in LIAG, resulting
in an increased ID/IG ratio and a reduced I2D/IG ratio. XPS was further
analyzed, as shown in Fig. S7. The atomic ratio of C/O sharply de-
creases from 16.10 in LIG to 4.03 in LIAG/KC-15 (Fig. 3f), which is
attributed to the carbon consumption and the increase of oxygen-con-
taining functional groups due to oxygen participation in the activation
process. Additionally, the sharp decline in the atomic ratio of C/N de-
monstrates the KOH activation can improve the amount of nitrogen
doping in LIAG, thus inducing pseudocapacitance behavior with high
electrochemical performance [58]. It is worth noting that in the con-
ventional method with an argon atmosphere, the KOH activation will
generally reduce the nitrogen content of the electrode. This is due to
metallic potassium is produced within carbon materials, resulting in the
intercalation of potassium between carbon materials [59]. However,
the increased nitrogen content in this work is due to the removal of the
product of K2O after samples rinsed with deionized water, and the
consumption of carbon element. Similar to the trend of LIAG/KC, LIAG/
KS possesses a sharp drop in the atomic ratio of C/O and C/N (Fig. S8a).
Detailed chemical composition analysis of nitrogen from the fitting of
XPS N 1s spectra (Fig. S9) was conducted to investigate the effect of
KOH activation, as shown in Fig. 3g. The chemical composition of
pyrrolic N increases from 0 to 15 μL but decreases with the increase of
KOH. As for the pyridinic N and Quaternary N, opposite trends can be
obtained. Similar behavior was also found in different concentrations of

Fig. 3. KOH amounts/concentrations effect on physicochemical properties of LIAG. Raman spectra of (a) LIAG/KC-X and (b) LIAG/KS-Y. Summaries of ID/IG, I2D/IG
ratios and FWHM of G peak in Raman spectra of (a) LIAG/KC-X and (b) LIAG/KS-Y. (e) Correlations of the crystalline size along the a axis (La) with KOH amount/
concentration. (f) The C/O and C/N ratio derived from the XPS survey of LIAG/KC-X. (g) Chemical compositions of LIAG/KC derived from the fitting of XPS N 1s
spectra of LIAG/KC-X. (h) Sheet resistance (Rs) and (i) thickness of LIAG as a function of KOH amount/concentration.

6
H. Liu, et al. Chemical Engineering Journal 393 (2020) 124672

KOH (Fig. S8b), which indicates medium concentrations of KOH con-
tributes to the improvement of pyrrolic N atom thermodynamically
stable at the edges of graphene lattice, while higher KOH is more
beneficial for the stability of pyridinic and quaternary N atoms.
The chemical structure and composition of LIG/LIAG play a sig-
nificant role in controlling its sheet resistances (Fig. 3h). Compared to
LIG (17.76 Ω per square), LIAG/KC-5 or LIAG/KS-240 possesses low-
graphitic carbon and more porous structure, resulting in a higher sheet
resistance (21.93 or 21.66 Ω per square, respectively). The sheet re-
sistance slightly increases to 22.12 or 21.79 Ω per square owing to the
formation of more porous structure of quality-improved graphene as
KOH increases to 15 μL or 560 g/L, respectively. When KOH further
increases to 35 μL or 1020 g/L, a significant rise in sheet resistance can
be observed due to the overactivation of LIG. Combined with the
thickness of LIAG in Fig. 3i, its conductivity is plotted in Fig. S10. LIAG
has a decreased conductivity with the increase of KOH, but still has a
good conductivity of > 5.75 S/cm. It is worth noting that LIAG/KC has
thicker thickness than LIAG/KS because KOH crystal will totally mix
with LIG at the laser contact scanning (Fig. S1d) while only a thin layer
of KOH solution film participates in the reaction owing to the fluidity of
KOH solution during processing.
Inspired by the advantages of LIAG, 16 interdigitated LIAG elec-
trodes were fabricated and packaged into LIAG-IMSC devices with
hydrogel electrolyte. To demonstrate their electrochemical perfor-
mance, we performed CV and GCD tests of devices from LIAG/KC-X and
LIAG/KS-Y. Fig. 4a,b shows the CV profiles at a scan rate of 20 mV/s,
which exhibit stable quasi-rectangular shapes for strong electro-
chemical double layer capacitors (EDLC) characteristics. Other CV
profiles at different scan rates (10 to 100 mV/s) are presented in Figs.
S11 and S12. With the increase of KOH, the CV shapes are distorted at
high scan rates, especially at high KOH amount/concentration (> 15 μL
or 560 g/L), which is due to the decreased conductivity of LIAG elec-
trodes (Fig. S10). From Fig. 4c,d, all the GCD curves of LIAG/KC-X and
LIAG/KS-Y at a current density of 0.1 mA/cm2 show a nearly triangular
shape, corresponding to the CV curves. Figs. S13 and S14 further dis-
play the GCD curves at different current densities with small voltage
drops and nearly symmetric charging and discharging curves, further
confirming the good EDLC behavior of the devices. Fig. 4e,f plots the
areal capacitances of LIAG/KC-X and LIAG/KS-Y, respectively, which
suggest the increased areal capacitance with the increasing KOH
amount/concentration. It is worth noting that the capacitive perfor-
mance of the devices is mainly determined by the key factors of the
structure and physicochemical properties of LIAG, such as the number
and diameter of pores and atomic defects on LIAG, the crystalline size
along the a axis (La), the C/O and C/N ratio, the thickness and wett-
ability of LIAG. Since LIAG/KC-35 or LIAG/KC-1020 has significant

Fig. 4. Electrochemical performance of LIAG-IMSC devices in PVA/H3PO4 electrolyte. CV curves of (a) LIAG/KC-X and (b) LIAG/KS-Y at a scan rate of 20 mV/s. GCD
curves of (c) LIAG/KC-X and (d) LIAG/KS-Y at a current density of 0.1 mA/cm2. Areal capacitances of (e) LIAG/KC-X and (f) LIAG/KS-Y over a current density
ranging from 0.05 to 0.5 mA/cm2. (g) Areal capacitance comparison of LIAG/KC-X and LIAG/KS-Y at a current density of 0.05 mA/cm2. (h) Nyquist plots of LIG,
LIAG/KC-35, and LIAG/KS-1020 with corresponding equivalent circuit model. Inset is the magnified region. (i) Cycling stabilities of LIAG/KC-15 and LIAG/KS-560 at
a current density of 0.2 mA/cm2.

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H. Liu, et al. Chemical Engineering Journal 393 (2020) 124672

meso-, macropores (Fig. S2), considerable number of atomic defects,
low C/O and C/N ratio, maximum cross-section thickness and excellent
wettability, the maximum capacitance of LIAG occurred at 35 μL or
1020 g/L. In addition, the loss rate of areal capacitance in higher KOH
amount decreases with the increasing current densities from 0.05 to
0.5 mA/cm2 (78.0% loss for LIG, 64.6% loss for LIAG/KC-5, and only
36.5% loss for LIAG/KC-35). Similar behavior can be achieved for the
LIAG/KS-Y, strongly indicating good rate capability of LIAG-IMSC de-
vices. To understand the effect of KOH amount/concentration on the
electrochemical performance, the areal capacitances of LIAG at
0.05 mA/cm2 were plotted in Fig. 4g. As can be seen, there is a little
difference between KOH crystal and KOH solution. Specifically, the
areal capacitance of LIAG/KC has a nearly linear relationship with the
increasing KOH crystal from 0 to 35 μL. While, the areal capacitance of
LIAG/KS have an approximate inverted parabola relationship with the
increasing KOH concentration from 0 to 1020 g/L. LIAG/KC-35 and
LIAG/KS-1020 have the maximum areal capacitances of 30.06 and
32.00 mF/cm2 (0.05 mA/cm2), respectively, which are much (6 or 6.4
times) larger than that of conventional LIG electrodes (~5.0 mF/cm2)
without the activation process.
To further evaluate the electrochemical behavior of LIAG-IMSC
devices, EIS measurement was performed and the Nyquist plots from
LIG, LIAG/KC-35, and LIAG/KS-1020 with fitted equivalent circuit
model are shown in Fig. 4h and Fig. S15. Here, the parameters Re, Rct,
and Zw refer as the internal equivalent series resistance (ESR) of the
electrolyte and electrode, interfacial charge transfer resistance and
Warburg impedance, respectively. In the low-frequency region, the
Nyquist plots of LIAG/KC-35 and LIAG/KS-1020 are much closer to a
vertical line parallel to the Z-imaginary axis than that of LIG, suggesting
better capacitive behavior of LIAG-IMSC devices. In the high-frequency
region, the intercepts on the Z-real axis for the three devices are be-
tween 120 and 170 Ω (Table S1), exhibiting a small ESR. Additionally,
compared with LIG, LIAG/KC-35 and LIAG/KS-1020 have a shorter
semicircle and Warburg regions at high- and intermediate-frequency,
revealing smaller Rct and Zw and a better ion diffusion efficiency. This is
due to that LIAG/KC-35 and LIAG/KS-1020 have more significant
meso-, macropores with considerable number of atomic defects, thus
providing a better access to ion channels without ion shell desolations
[60]. In addition, the cycling stabilities of the devices from LIAG/KC-15
and LIAG/KS-560 were tested, as shown in Fig. 4i. After 6000 cycling of
GCD, LIAG/KC-15 and LIAG/KS-560 show the cycling stability with
capacitance retentions of 95.73% and 94.79%, respectively. The re-
sulting good cycling stability could be attributed to good wettability
and stable interface between the hydrogel electrolyte and electrodes.

Fig. 5. Overall performance of LIAG-IMSC devices. CV curves and capacitance retentions of (a) LIAG/KC-25, and (b) LIAG/KS-560 under bending angles from 0° to
180° at a scan rate of 20 mV/s. Inset in (a) is the schematic diagram of a device under bending. (c) Capacitance retention of LIAG/KC-25 and LIAG/KS-560 at different
bending cycles with a bending angle of ~90°. (d) CV curves at 20 mV/s, and (e) GCD profiles at 0.2 mA/cm2 of devices based on LIAG/KS-560 from 1 to 3 devices
connected in series. (f) CV curves at 20 mV/s, and (g) GCD profiles at 0.2 mA/cm2 of devices based on LIAG/KS-560 from 1 to 3 devices connected in parallel.
Photographs of a red LED powered by two serially-connected devices at 0.1 min (h) and 2 min (i).

8
H. Liu, et al.
From the GCD curves before and after cycling in Fig. S16, the increase
of IR drops and Coulomb efficiency can also be detected after cycling,
due to the inevitable collapse of some pores and more ions penetrating
into the micro-, mesopores, respectively.
To test the flexibility of LIAG-IMSC devices, we obtained CV mea-
surements of devices from LIAG/KC-25 and LIAG/KS-560 at 20 mV/s
under different bending angles from 0° to 180° and various bending
cycles with a bending angle of ~90°, respectively (Fig. 5a,b). All the CV
curves under various bending angles are nearly the same with almost
100% capacitance retention. In addition, after 10,000 bending cycles,
the capacitance attenuation was 18% and 13%, respectively, indicating
both LIAG and hydrogel electrolyte have good mechanical flexibility
(Fig. 5c). To meet the requirements of high voltage and specific energy
in practical applications, multiple devices from LIAG/KS-560 and
LIAG/KC-25 were amplified and assembled with series and/or parallel
connections. For comparison, the CV and GCD curves of one single
device were also provided. The operating voltages of both the CV and
GCD curves (Fig. 5d,e, Fig. S17a and b) increase linearly with 1.0 V for
a single device, 2.0 V for two devices and 3.0 V for three devices
connected in series with good consistency. Additionally, the currents of
the CV curves and discharge time of the GCD profiles (Fig. 5f,g, Fig.
S17c and S17d) have the linear increase relationship with the number
of devices in parallel. These results are consistent with the ESR values
increase from ~140 ± 10 Ω for one device to ~280 ± 20 Ω for two
serially-connected devices and 70 ± 5 Ω for two parallel-connected
devices by increasing the number of devices (Fig. S18). Two serially
connected LIAG-IMSC devices could easily drive a red light-emitting
diode (LED) and last for about two minutes (Fig. 5h,i). These device
integration behaviors demonstrate that the device is a good candidate
for practical applications.
Fig. 6 shows the Ragone plot of IMSC devices from LIAG/KC-35 and
LIAG/KS-1020 to compare their areal energy and power densities with
other LIG-based IMSC devices. The LIAG devices exhibited an excellent
areal energy density of 4.01 μWh/cm2 for LIAG/KC-35 and 4.27 μWh/
cm2 for LIAG/KS-1020, which are 6.27 and 6.67 times higher than
those from LIG at 0.05 mA/cm2, and 12.04 and 11.65 times higher at
0.4 mA/cm2, respectively. Most importantly, their areal energy den-
sities are higher than those of reported LIG-based and some RGO-based
IMSC devices (Table S2), including LIG in 1 M H2SO4 (Ref. [10]),
SPEEK-based LIG in 1 M Na2SO4 (Ref. [24]), LIG in PVA/H2SO4 (Ref.
[61]), lignin/PVA-based LIG in PVA/H2SO4 (Ref. [25]), B-doped LIG in
PVA/H2SO4 (Ref. [28]), Fs-LIG in PVA/H2SO4 (Ref. [33]) and Ar-pro-
cessed LIG with air-plasma treatment in PVA/H2SO4 (Ref. [30]). The
excellent capacitance of the IMSC devices from LIAG/KC-35 and LIAG/
Fig. 6. Ragone plots of IMSC devices from LIAG/KC-35, LIAG/KS-1020 and
LIG-based electrodes with various electrolytes.
9
Chemical Engineering Journal 393 (2020) 124672
KS-1020 is mainly contributed to: (1) The hierarchical porous structure
with considerable micro-, mesopores appeared on the walls of macro-
porous graphene and carbon atomic defects, which allow the hydrogel
electrolyte to penetrate and uniformly coat on the electrode surface; (2)
the slightly increased nitrogen content (4.94% for LIAG/KC-35) and
increased specific surface area after activation helps improve the
pseudocapacitance and EDLC behavior of electrodes, respectively; (3)
the improved wettability (hydrophilic or even superhydrophilic) be-
tween electrodes and electrolyte help ions penetrate more easily into
porous materials; (4) the increased thickness of electrodes after acti-
vation enable storage more ions; and (5) the good electronic con-
ductivity of the laser-induced and KOH-activated 3D graphene that
facilitates charge transport and current collection.
It is worth noting that most previous works listed in Table S2 rely on
high-precision, high-cost laser, post-plasma treatment, inert gas atmo-
sphere, or complex preparation procedure of electrode material. In
contrast, this work produces activated 3D porous graphene in one-step
under room temperature and ambient atmosphere by a low-cost CW
CO2 laser. Therefore, this method provides a rapid route to enhance the
performance of carbon-based materials for flexible and wearable elec-
tronics and has great potentials for roll-to-roll production.
4. Conclusions
In summary, we report a synchronous induction and activation
method in one-step to prepare porous LIAG via a low-cost CW CO2 laser.
We have studied the effects of KOH concentrations on the porous mi-
crostructure, nitrogen content, lattice size and wettability. Studies re-
veal that medium concentrations of KOH are able to improve the
quality, heteroatoms doping and wettability of porous graphene in
comparison with lower KOH. And high concentrations of KOH con-
tribute to the formation of carbon atomic defects and mesoporous
structures with increased content of nitrogen. LIAG/KC-based IMSCs
has a nearly linear relationship with the increasing KOH from 0 to
35 μL, and LIAG/KS-based IMSCs increases non-linearly as the KOH
concentration increases from 0 to supersaturation. The resulting LIAG-
IMSCs have the energy density of 4.27 μWh/cm2, which is much higher
than reported LIG-based IMSCs. They also have good cycling stability,
mechanical flexibility under bending tests, and modular integration
capability in series and/or in parallel connections. More importantly,
this activation methodology developed here is a new method, which
provides a new, rapid route to enhance the performance of carbon-
based materials for flexible and wearable electronics. Depending on the
high performance of LIAG materials, it has great potentials in various
applications of flexible energy storage electronics.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The current study was supported by the National Natural Science
Foundation of China (No. 51905178), the Natural Science Foundation
of Guangdong Province, China (No. 2018A030310396, No.
2014A030312017), and the Fundamental Research Funds for the
Central Universities, China. The authors also thank Ms. Shimin Huang
for XPS spectra measurements, Ms. Xiting Liu and Mr. Zhiqiang Qiu for
electrochemical tests, Mr. Xiaofei Zhang for discussions with KOH ac-
tivation mechanism, and Ms. Wanwen Liang for BET analysis.
H. Liu, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.124672.
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