Journal of Alloys and Compounds 860 (2021) 157898

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Achieving superior energy storage and microwave absorption by

simultaneously-controlling active heteroatoms and porosities in
carbon nanosheets
Shaobo Liu, Yuhui Peng, Qiang Han, Chenggang Yang, Lianwen Deng, Jianfei Zhou,
Xiaoliang Liu*
School of Physics and Electronics, Central South University, Changsha, 410083, PR China

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

Article history: Tailoring the carbon-electrode with rich porosities and heteroatoms has been demonstrated to break the
Received 27 August 2020 limitation of capacitive storage and microwave absorption, but the balance between them remains a
Received in revised form great challenge, resulting in the difficulty to control and utilize the active sites. Here, porous heteroatoms
16 October 2020
co- and tri-doping carbon nanosheets are easily achieved by a developed melting-pressing-carbonization
Accepted 7 November 2020
Available online 11 November 2020
(MPC) approach with the assistance of g-C3N4, which concurrently activates pore structure and surface
properties by serving as structure-directing agent, activating agent and nitrogen resource. The optimized
co-doping carbon nanosheet (NPCN-1) exhibits a novel surface structure containing high N (14.1%)
Keywords:
C3N4
contents with well-distributing conductive and redox-active N species, and ions-matched pores centered
Carbon nanosheets on 0.7 nm, which provides rich-effective active sites to capture fast electron and ion transport, reflected
Heteroatoms doping by the energy storage dynamics. Therefore, the NPCN-1 supplies a large specific areal capacitance of
Ions-matched pores 0.434 F m
2, even outperforming the graphene (0.21 F m
2) as supercapacitor electrode, and displays a
Supercapacitors broad effective absorption bandwidth of 6.64 GHz and a strong reflection loss of
44.5 dB in microwave
Microwave absorption absorption (MA). These energy storage and MA capability can be further enhanced after realizing tri-
doping of O, N and Fe2O3 by MPC strategy, shedding light on an avenue to future application and
development for the active materials.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
Advanced energy storage systems are immensely desired over
the world that needs more efficient, sustainable, and green energy
supplying [1e4]. Supercapacitor has aroused tremendous attention
as energy storage device by virtue of its prominent power density
with fast reaction dynamics, remarkable durability and excellent
safety [5e7]. However, the low energy density of supercapacitor
restricts its large-scale application, which stimulates the explora-
tion of electrode materials with improved charge storage capability
[8e10]. Recently, numerous researchers are keen on the amor-
phous carbon electrodes containing carbon spheres [11e13], carbon
sheets [14] and carbon foam [7,15] etc., among which the carbon
nanosheets have attracted extraordinary interest for improving
energy storage due to the extreme potential to generate lots of
* Corresponding author.
E-mail address: xl_liu@csu.edu.cn (X. Liu).
active sites, shorter ions diffusion length and face to face electronic
conductivity. For instance, an interconnected carbon nanosheets
was created by simple carbonization of hydrothermal product of
hemp, delivering a large specific capacitance of 106 F g
1 (10 A g
1)
in ionic liquids electrolyte because of large specific surface area and
high electrical conductivity [16]. Great efforts have been devoted
into elevating the capacitive performances of carbon nanosheet
electrodes, but the capacitance of them are still low.
The energy storage for carbon nanosheets is highly related to the
surface structure and chemical property, especially the porous
structures and heteroatoms doping [17e19]. Exactly, the micro-
pores can dedicate to large specific area for releasing active sites,
the mesopores can offer favorable ion-transport channels and the
macropores can server as ion reservoirs [20,21]. These porous
structures interconnected with micro-, meso- and macro-pores on
the carbon nanosheets can guarantee efficient and fast accessibility
of the electrolyte ions into the active sites, furnishing salient elec-
tric double layer capacitances [22]. For the heteroatoms doping

https://doi.org/10.1016/j.jallcom.2020.157898
0925-8388/© 2020 Elsevier B.V. All rights reserved.
S. Liu, Y. Peng, Q. Han et al.
such as N and O groups, they can not only contribute to extra
pseudocapacitance, but also induce surface charge redistribution
and improve the electrophilicity, surface wettability and interface
compatibility of electrode and electrolyte [23,24]. Thus, integrating
an interconnected porous structure and heteroatoms into the car-
bon nanosheets presents an efficient solution to enhance its energy
storage performance. However, it is very difficult to balance the
interconnected porous structures with dominated pore that
matches with the size of ions, and high levels doping of hetero-
atoms. Moreover, the exploration of the multiple synergistic effects
from the combination of these approaches on increasing the active
sites of carbon nanosheets is highly desired.
On the other hand, microwave absorption (MA) has drawn wide
attention due to daily-increased electromagnetic (EM) wave
pollution [25e27]. MA materials that absorb the incident EM wave
to convert into heat through dielectric or magnetic loss have
aroused tremendous research interest to resolve the pollution
problem [28e30]. Among various MA absorbents, carbonaceous
materials are particularly pursued as promising candidate because
of their large absorbing efficiency, tunable dielectric loss and
excellent stability [31]. Reported by Qi et al. [32], the CNT of metal-
free obtained by the K2CO3 catalyst exhibited a maximum reflection
loss (RL) value of
20.2 dB under 14.2 GHz. Xie’s group observed a
maximum RL of
20.17 dB under 7.24 GHz in a microcrystalline
graphene oxide [33]. There are also many researches on carbon
black for MA, among which Qin et al. shows the results
of
19.31 dB at 10.4 GHz delivered by the composite absorbent of
carbon black and ZnO whiskers [34]. Unfortunately, the MA per-
formances for these carbon material themself are still unsatisfied,
caused by the low specific surface area and highly-graphitized
surface that result in microwave absorption performance limited
[35]. On the other hand, compositing magnetic materials with them
supplies a strategy for an improved MA performance, but the
preparation processes are usually complex and time-consuming.
To obtain a prominent MA performance, regulating the structure
and surface property of the carbon materials is confirmed to be
highly-efficient [36e38]. For instance, tailoring the carbon absor-
bents with porous structure can not only prolong the paths for
microwave propagation which results in the electromagnetic en-
ergy loss, but also generate plentiful solid
air interfaces to reduce
EM wave energy [31,39]. Additionally, by introduction of the het-
eroatoms into the graphitic layers, the carbon material can be
endowed with multiple dipolar configurations to enhance the
performance of dielectric characteristics [40]. Inspired by those,
Yuan et al. prepared an N and S co-doped ordered mesoporous
carbon, achieving a maximum reflection loss value of
32.5 dB
under an effective absorption bandwidth of 3.2 GHz [37]. Until now,
unfortunately, the development of carbon absorbents by effective
regulation of structure and surface characteristics is still in infancy,
which remains a considerable challenge in achieving prominent
MA performance.
In this work, we demonstrate the successful fabrication of the
carbon nanosheets with simultaneously crafted hierarchical porous
architectures and high heteroatoms doping by using an easily-
developed melting-pressing-carbonization (MPC) approach. The
process of MPC is firstly carried out by homogeneous blend of the
glucose and the moist graphitic carbon nitride (g-C3N4), as shown
in Fig. 1a. The obtained mixture is further conducted at 180  C to
melt glucose, followed by pressing with a certain pressure of 25 N
to enable the glucose resin and g-C3N4 highly cross-linking layer-
by-layer, which is then carbonized under high-temperature to
receive the carbon nanosheets without an additional template
removal. The carbon nanosheets products with the structures
including morphologies and porosity, and surface doping of N and
O can be simultaneously regulated by changing the contents of g-
2
Journal of Alloys and Compounds 860 (2021) 157898
C3N4 precursor. The optimized carbon nanosheet (NPCN-1) with
the precursor ratio of 1 of g-C3N4 to glucose occupies 0.7 nm-
dominated hierarchical porous structure, large specific surface area
(565 m2 g
1) and high N (14.1%) and part O (3%) contents. It exhibits
not only large specific capacitance (0.434 F m
2) and excellent rate
performance (70.6% from 0.5 to 20 A g
1) for supercapacitor elec-
trode but also broad effective absorption bandwidth (6.64 GHz) and
strong reflection loss (
44.5 dB) for microwave absorption. These
performances can be further improved by further doping with trace
of Fe2O3 prepared nearly with the same process. Our work elabo-
rates the rational design of carbon material from the surface en-
gineering about the structure property, which can be extended to
other advanced materials for energy storage and transition as well
as microwave absorption fields.
2. Experimental
2.1. Material synthesis
2.1.1. Fabrication of g-C3N4
g-C3N4 was prepared by a simple calcination of 12 g urea sealed
in a corundum crucible with tinfoil. The crucible containing urea
was heated to 550  C with the heating rate of 5  C min
1 in a
furnace, maintaining for 2 h, which obtains the product of g-C3N4
(Fig. S1a) after cooling under room temperature.
2.1.2. Fabrication of NPCN-1
1 g of the as-prepared g-C3N4 was firstly dispersed into 40 mL
deionized water, continuously stirring for 0.5 h under room tem-
perature, and then filtrated by suction filter. The moist g-C3N4 was
homogeneously blended with 1 g of glucose, and the mixture of
them was then putted into a furnace with 180  C. After heating for
10 min, the mixture was removed to room temperature environ-
ment, which was pressed for 5 min by a Teflon-lined autoclave of
2.5 kg and then putted into the furnace again, followed with the
same treatment twice. The as-derived g-C3N4@glucose resin was
then carbonized at 800  C for 2 h. After washing with deionized
water and drying at 70  C overnight, we obtained the final N-doped
carbon, labeled as NPCN-1. The control experiments were also
conducted with the same preparation procedure as the NPCN-1,
except for using 0.2 g and 0.5 g g-C3N4 to substitute for 1 g g-
C3N4 precursors, which obtained the samples denoted as NPCN-0.2
and NPCN-0.5, respectively. The glucose-generated carbon block
(GCB) was prepared by directly carbonizing the glucose at 800  C
for 2 h.
2.2. Materials characterization
The morphology of the samples was characterized by a MIRA3
TESCAN scanning electron microscopy (SEM). Transmission elec-
tron microscopy (TEM) image was measured with a FEI Talos-S
instrument. X-ray photo-electron spectroscopy (XPS) was recor-
ded using ESCALAB Xiþ. A LabRAMHR-800 system with 532 nm
excitation wavelength was applied to obtain Raman spectra. X-ray
diffraction (XRD) spectrum taken on a SIEMENS D500 diffractom-
eter was performed under Cu Ka radiation with l ¼ 0.15056 nm N2
adsorption-desorption isotherms at 77 K was tested by an AUTO-
SORB IQ instrument, with the data analyzed by BET and QSDFT
methods.
2.3. Electrochemical measurements
Three electrode configuration: the work electrode was prepared
by evenly coating the mixture of the as-obtained material,
conductive acetylene black, and poly(tetrafluoroethylene) (PTFE)
S. Liu, Y. Peng, Q. Han et al. Journal of Alloys and Compounds 860 (2021) 157898

Fig. 1. Microstructure evolution of the NPCNs: (a) illustration of the processes of MPC method to synthesize NPCN-1; SEM patterns of (b) GCB, (c) NPCN-0.2, (d) NPCN-0.5 and (e)
NPCN-1; (f) TEM and (g) HRTEM of NPCN-1; (h) HAADF-STEM image of NPCN-1 and (iej) corresponding element mapping of N and O.

binder at a weight ratio of 8:1:1 on nickel foam. With the Pt plate cell were determined by the equations below:
counter electrode and Hg/HgO reference electrode, the measure-
ment of the electrochemical performance for the work electrode I Dt
Cc ¼ (2)
was performed by a CHI 660E workstation in a three-electrode mDV
system containing 6 M KOH electrolyte. Cyclic voltammograms
(CV) curves and galvanostatic charge/discharge (GCD) curves were Cc D V 2
Ec ¼ (3)
recorded within -1-0 V with the sweep rate range from 10 to 7:2
300 mV s
1 and current densities of 0.5e20 A g
1, respectively.
Electrochemical impedance spectroscopy (EIS) tested over the Ec *3600
frequency range of 0.01e100 kHz was obtained by applying an Pc ¼ (4)
Dt
amplitude of 5 mV. The specific capacitance (Cs, F g
1) of the work
electrode was calculated by the discharge curves, using the where I (A) is the discharge current, m (g) gives the total active
equation: mass, Dt (s) represents the discharge time, and DV (V) denotes the
work potential window of the cell.
I Dt
Cs ¼ (1)
mDV
2.4. Microwave absorption measurements
where i (A), Dt (s), m (g) and DV (V) denote the applied discharge
current, the discharge time of the GCD curves, the active material The permittivity parameters of the coaxial samples were
mass (about 2 mg) and the operate voltage, respectively. measured using a microwave vector network analyzer (N5230A,
Symmetric supercapacitors: two pieces of the work electrodes Agilent) in the frequency range from 2 to 18 GHz. The test samples
were assembled in a 2032 coin cell, accompanied with a membrane with 20 wt% were uniformly blended with the paraffin and then
separator and 6 M KOH electrolyte. The gravimetric specific pressed into a toroidal ring with outer and inner diameter
capacitance (Cc, F g
1), gravimetric specific energy density (Ec, Wh respectively of 7.0 and 3.04 mm. The microwave RL (dB) was
kg
1) and gravimetric specific power density (Pc, W kg
1) for the calculated by:
3
S. Liu, Y. Peng, Q. Han et al.




Z
Z 0

RLðdBÞ ¼ 20lg

in
(5)
Zin þ Z0

rffiffiffiffiffi


Zin mr
2pfd pffiffiffiffiffiffiffiffiffi

¼ tanh

j mr εr


Z0 εr c
where Zin denotes the input impedance of absorber, Z0 is the
impedance of air, f is the frequency of microwaves, d represents the
thickness of the absorbing materials, and c is the velocity of the
electromagnetic (EM) wave in free space.
3. Results and discussion
3.1. Characterization of the samples
The microstructure evolution of the N-doping porous carbon
nanosheets affected by g-C3N4 was examined by SEM, recorded in
Fig. 1. In the absence of g-C3N4, the product GCB of alone glucose
after carbonization is large carbon block (Fig. 1b), with the highly-
inhomogeneous size from hundreds of nanometers to tens of mi-
crons. When mixing the g-C3N4 with glucose at the ratio of 0.2
under the assistance of MPC process, the obtained NPCN-0.2
(Fig. 1c) clearly turns to be the morphology that consists of nano-
particles in which partial nanosheets appear at the edge, indicating
largely-decreased size compared with that of GCB. With further
increasing the ratio to 0.5, nearly total carbon nanosheets in Fig. 1d
can be received by NPCN-0.5. The sheet-like structure of NPCN can
be further optimized by controlling the ratio to be 1. In NPCN-1, as
given in Fig. 1e, we can obtain the loosely-stacked thin-layered
carbon nanosheets with abundant macropores in between them,
which can be further verified by the TEM image in Fig. 1f. The
thickness of carbon nanosheets shown in TEM is about 8 nm, in line
with the result determined by the atomic force microscope (AFM)
in Figs. S1b and 1c. These results suggest that the g-C3N4 is well
cross-linked with the glucose layer-by-layer during the melting-
pressing process, and it can further effectively regulate the for-
mation of carbon nanosheets by serving as the structure guide
agent in the followed carbonization. Such regulation effect may be
further reflected by the changes of optical image of NPCN-1 relative
Fig. 2. Surface element composition and chemical states regulation: (a) XPS survey spectra of GCB, NPCN-0.2, NPCN-0.5 and NPCN-1; high-resolution N 1s spectra of (b) NPCN-0.2,
(c) NPCN-0.5 and (d) NPCN-1 (inset: schematic chemical structure); (e) high-resolution O 1s spectra and (f) contact angle of KOH solution on NPCN-1 under different times.
Journal of Alloys and Compounds 860 (2021) 157898
to that of GCB (Figs. S1dee). Interestingly, the g-C3N4 doesn’t
require an extra removal because there is nothing obtained when
carbonizing g-C3N4 at 800 , making this MPC approach highly-
scalable.
The carbon nanosheets of NPCN-1 are further measured by the
(6) high resolution TEM (HRTEM) in Fig. 1g, from which rich amor-
phous region with a little short-range ordered microcrystalline can
be clearly found, conductive to providing more surfaces to exposure
active sites and shorten the electrons transport distance. Moreover,
the element mapping in Fig. 1hej shows the doped N and O
distributing uniformly over the carbon nanosheets, implying the
successful modification of the NPCN-1 by N and O.
To further detect the surface element composition and its cor-
responding chemical states in the as-obtained samples, analysis of
XPS spectra were provided [41]. As presented in Fig. 2a, in addition
to C and O elements that the GCB only contains, N element can be
observed in all the NPCN samples, further confirming the g-C3N4
can act as N source to successfully incorporate N into the carbon
lattice. The amounts of N in NPCN-0.2, NPCN-0.5 and NPCN-1 are
5.0%, 14.0% and 14.1%, respectively. Revealed by the high-resolution
N 1s spectra (Fig. 2bed), three identical kinds of N including pyr-
idinic N (N-6), pyrrolic N (N-5) and quaternary N (N-Q) can be
assigned for the NPCN samples, at about 398.1, 399.7 and 400.8 eV,
respectively [42,43]. Particularly, an additional N state at 404.0 eV
attributed to oxidized N (N-X) can also be discerned in the NPCN-
0.5 and NPCN-1 (Fig. 2c and d), which confirms a strong interac-
tion between the O and N in them, beneficial to obtaining more
positive-charged N to accelerate electron transfer [44]. It has been
reported that N-5 and N-6 on the surface of carbon framework are
pseudocapacitive sites, while the presence of N-Q and N-X helps to
enhance its electronic conductivity [45,46]. In NPCN-1, the amounts
(Table 1) of N-6, N-5, N-Q and N-X are 6.43%, 2.66%, 4.74% and
0.27%, respectively, offering a solid basis to promote electron to
reach the pseudocapacitive sites and thus contributing to pseudo-
capacitance by faradaic redox reactions [47]. In Fig. 2e, partly doped
O (3%) in NPCN-1 can be fitted as three peaks corresponding to C]
O (531.4 eV), CeO (532.4 eV) and OeC]O (533.5 eV) [48]. These O-
containing groups are demonstrated to not only improve the sur-
face wettability at the interface of electrode and electrolyte to
decrease the interface transfer resistance for ions, but also offer
4
S. Liu, Y. Peng, Q. Han et al.
Table 1
Proportion of the different N species in the samples.
Samples Total N (%) N-6 (%) N-5 (%) N-Q (%)
NPCN-0.2 5 2.05 1.15 1.8
NPCN-0.5 14 6.1 2.2 4.54
NPCN-1 14.1 6.43 2.66 4.74
additional pseudocapacitance [49]. Fig. 2f indicates the contact
angle of KOH solution on NPCN-1 under different times, and a
complete infiltration of KOH with the contact angle of 0 after 2s
demonstrates superior surface wettability of NPCN-1.
The porous features of the NPCN-1 involved of the specific
surface area and pores distribution are further explored with ni-
trogen adsorptionedesorption isotherms measurements. Observed
from Fig. 3a, the NPCN-1 displays typical IV type isotherm together
with H1 type hysteresis loop, meaning the co-existence of meso-
and micro-pores [50]. However, negligible N2 uptake is found in the
isotherm of GCB, indicative of smooth surface without pores. Ac-
cording to the nonlocal density functional theory, the specific sur-
face area of NPCN-1 is 565 m2 g
1, more than 26 fold relative to that
of GCB (21.6 m2 g
1). The remarkable improvement for the surface
pores in NPCN-1 can be further confirmed by the detailed infor-
mation on pores size distribution. As exhibited in Fig. 3b, the NPCN-
1 absorbs the N2 nearly from 0.6 to 35 nm with large volumes of
1.15 cm3 g
1, while it is difficult to distinguish the N2 absorption
volumes in GCB. These results in combination with the SEM and
TEM images in Fig. 1 demonstrate that the introduction of g-C3N4 in
the MPC processes of glucose can activate the carbon products,
promoting the generation of abundant micro-, meso- and macro-
pores. The pores activation of NPCN-1 by g-C3N4 may derive
from: (1) the pre-existence coarse sites and pores on g-C3N4 serving
Fig. 3. Development of surface porosities and crystallinity: (a) Nitrogen adsorptionedesorption isotherms, (b) pores size distribution, (c) XRD and (d) Raman spectra for GCB and
NPCN-1.
Journal of Alloys and Compounds 860 (2021) 157898
as opposite direction template for forming template pores during
glucose carbonization; (2) the generation of large amounts of gases
N-X (%) caused by g-C3N4 decomposition leading to the construction of new
0
pores and enlarging the template pores; (3) the doping of N,
1.16 especially in the form of N-Q, prohibiting the pores from self-
0.27 healing under high temperature due to its stereoscopic character-
istic. Interestingly, the activated pores in NPCN-1 display the
dominated concentrations at the size of 0.7 nm, which is demon-
strated to be the optimal size to match ions to exhibit the largest
electronic double layer capacitance in aqueous electrolyte owing to
the exceptional compatibility with the electrolyte ions [51].
The crystallinity of the NPCN-1 can be further disclosed by the
XRD and Raman spectra. From the XRD images in Fig. 3c, it is found
that the NPCN-1 indicates two analogous peaks indexed to (002)
plane at ~25 and (100) plane at ~43 with those of the GCB,
affirming a complete decomposition of g-C3N4 [23,52]. Compared
with that of the GCB, the (002) plane of NPCN-1 shifts to a larger
diffraction angle, which corresponds to a decreased interlayer
distance and is probably ascribed to the removal of oxygen in the
interlayer, beneficial to the electron transfer along the c axis. As for
the (001) planes, an obviously enlarged half-height width is
observed in NPCN-1, showing the amorphous attribute with
decreased crystalline, in line with the results provided by Raman
spectra [53,54]. In Fig. 3d, the D band at 1345 cm
1 and G band at
1587 cm
1 of the Raman spectra are respectively aroused by the
defective structure and hexagonal graphite in carbon material, and
the value for ID/IG is generally used to evaluate the defect density
for carbon materials [55]. By contrast, the NPCN-1 presents a
distinctly larger ID/IG of 1.06 than 0.7 of GCB, unveiling the presence
of rich defects in NPCN-1, which are highly associated with the
porous structures and heteroatom doping, desirable for applying as
supercapacitor electrode and microwave absorption [56e58].
5
S. Liu, Y. Peng, Q. Han et al.
3.2. Characterization of the electrochemical performances of the
samples
To examine the capacitance storage ability of the as-obtained
samples, a three electrode configuration containing 6 M KOH
electrolyte was conducted using them as work electrodes, while
reference and counter electrodes were Hg/HgO electrode and
platinum plate, respectively. The CV pattern of NPCN-1 with the
scan rate from 10 to 300 mV s
1 is evaluated in Fig. 4a. All curves
indicate quasi-rectangular shapes and maintain well after a 30 fold
magnification of the sweep rate, suggesting a prominent capacitive
behavior and rate performance. The part deformation observed in
the curves and shown by bumps demonstrate the generation of
additional pseudo-capacitance from the Faradaic redox reaction of
N and O groups such that there is a synergistic contribution of the
porous structure and heteroatom doping to the total capacitance
[45,55]. Shown in Fig. 4b, highly symmetrical and linear GCD curves
of NPCN-1 disclose excellent reversibility, and the little IR drop
indicates low internal resistance that is beneficial for reducing
energy loss [59,60]. Fig. 4c gives a comparison of the CV response
for GCB, NPCN-0.2, NPCN-0.5 and NPCN-1 at 10 mV s
1. Among
them, the largest area and peak current can be obtained in the
Fig. 4. Electrochemical performances evaluation in three electrode system: (a) CV curves at various scan rates and (b) GCD curves at different current densities of NPCN-1; (c) CV
curves under 10 mV s
1, (d) GCD curves under 1 A g
1; (e) comparison of areal specific capacitances and (f) rate performances of the GCB, NPCN-0.2, NPCN-0.5 and NPCN-1.
6
Journal of Alloys and Compounds 860 (2021) 157898
NPCN-1, which implies its prominent charge storage capability, in
agreement with the longest discharge time in Fig. 4d. The detailed
specific capacitance of NPCN-1 at 0.5 A g
1, calculated with equa-
tion (1) based on the discharge curve in Fig. 4d, is 245 F g
1,
apparently higher than those of NPCN-0.5 (224 F g
1), NPCN-0.2
(160 F g
1) and GCB (55 F g
1). Normalized with the specific sur-
face area in Fig. 4e, an areal specific capacitance of 0.434 F m
2 can
be achieved for the NPCN-1, suggesting the efficient application of
its surface for energy storage and even outperforming the theo-
retical capacitance of graphene (0.21 F m
2) and those of the
preciously-reported carbons activated by the corrosive activators
(Table S1) such as N and O co-doped carbon (0.276 F m
2) [55],
compressing carbon nanocages (0.08 F m
2) [61], N-doped porous
carbon nanosheets (0.307 F m
2) [58], and macroalgae-derived
carbon (0.1 F m
2) [62]. When enlarging the current density to
20 A g
1, as displayed in Fig. 4f, a specific capacitance of 173 F g
1 is
still retained with a retention rate of 70.6%, but only 96, 77 and
3 F g
1 are observed for NPCN-0.5, NPCN-0.2 and GCB, respectively.
This further confirms the superior rate performance of NPCN-1,
implying the fast transfer matching for electron and ion. After
cycling charge and discharge over 10000th at 10 A g
1, 93.6% of the
initial capacitance (Fig. S1f) is remained for the NPCN-1, suggesting
S. Liu, Y. Peng, Q. Han et al.
a good stability.
EIS for the samples was explored over the frequency range from
0.01 to 105 Hz to reveal the electron and ion transport kinetics. As
shown in Fig. 5a, all samples exhibit the Nyquist plots composed of
the intercepts on Z0 in high frequency reflecting effective series
resistance (Rs), semicircles in middle-high frequency with the
diameter depicting charge transfer resistance (Rct) and slope lines
in low frequency induced by the ions diffusion [63]. In comparison
with the other three samples, the NPCN-1 clearly provides an
approximately-vertical line with phase angle of 84.2 in low fre-
quency region and the smallest Rct (~0.05 U, obtained by the fitting
circuit) in middle-high frequency, which indicates much better
capacitance response with faster ion and electron transfer than
NPCN-0.5, NPCN-0.2 and GCB. From Fig. 5b, the largest character-
istic frequency of 0.33 Hz is found for the NPCN-1 at
45 , further
demonstrating the fast response to electron and ion. Shown in
Fig. S2, we have correlated the specific capacitances with the sur-
face area and surface charge transfer resistance, from which it can
be deduced that the specific capacitance can be effectively opti-
mized with increasing the surface area accompanied with reducing
the charge transfer resistance and trends to balance until the spe-
cific surface area over 500 m2 g
1. This result confirms the charge
storage capability of the electrodes can be simultaneously influ-
enced by the surface area and surface charge transfer resistance.
The charge storage kinetics about the NPCN-1 is subsequently
determined by estimating the contribution of capacitive and
diffusive behavior by CV tests at 5e80 mV s
1. Generally, the
relationship of scan rate with corresponding current density at a
fixed potential (
0.5 V in our case) is reflected by Refs. [64].
Fig. 5. Research on transfer kinetics of electron and ion: (a) Nyquist plots and (b) Bode plots of GCB, NPCN-0.2, NPCN-0.5 and NPCN-1; (c) Randles-Sevcik plot at
0.5 V, (d)
separation of capacitive and diffusive contributions of CV curve at 5 mV s
1, (e) contribution proportion of capacitive and diffusive processes to total capacitance under various
sweeping rates, (f) ex-situ Raman at
1 V and (g) illustration of the transport of the electron and ion on the NPCN-1.
7
Journal of Alloys and Compounds 860 (2021) 157898
rffiffiffiffiffi  
Zin mr 2pfd pffiffiffiffiffiffiffiffiffi
¼ tanh j mr εr (7)
Z0 εr c
where a and b are the adjustable parameters, and b locates between
0.5 and 1, with 0.5 showing a diffusive nature while 1 meaning an
entire capacitive behavior of the energy storage process. Deduced
from Fig. 5c, the values of b are 0.93 and 0.97 for anodic and
cathodic processes, respectively, which discloses a combined
contribution from capacitive and diffusive behavior in NPCN-1.
The quantitative proportion of the capacitive and diffusive
contribution versus the total capacitance can be further obtained
relying on the equation below [65].
iðVÞ ¼ k1 nþk2 n1=2 (8)
where k1 and k2 are the coefficients that respectively represent
surface capacitive- and diffusion-controlled processes. The result
(Fig. 5d) shows that the proportion of the two processes at 5 mV s
1
are 75.2% and 24.8%, respectively, which change into 93.7% and 6.3%
with increasing the scan rate to 80 mV s
1 (Fig. 5e). The dominant
surface capacitive contribution reveals that the NPCN-1 possesses
fast charge storage kinetics, further demonstrating that the prom-
inent surface pores structure and high N doping are beneficial to
fast electron and ion transfer. In Fig. 5f, the Raman spectrum shows
the value of ID/IG for NPCN-1 decreases to 0.94 after discharging
to
1 V, which could be ascribed to the effective immersion of ion
into the defect and pore sites [66].
Based on the analyses above, the possible mechanism for the
S. Liu, Y. Peng, Q. Han et al.
enhanced transport for electron and ion in the NPCN-1 should be:
(1) oxygen groups promoting Kþ ions immersion into the pores and
defects; (2) the interconnected nanosheets structure that can not
only supply multiple electron transport route, but also form mac-
ropores to serve as ion-buffer reservoirs; (3) concentrated pores
distribution at 0.7 nm facilitating the desolvation of Kþ ions to
efficiently immerse into the active sites [51]; (4) high N doping
coupled with abundant N-Q and N-X species benefitting to the
improved conductivity. These fast electron and ion transfer kinetics
in NPCN-1 with increased specific surface area (Fig. 5g), therefore,
contributes to the enhanced energy storage. Due to these rich active
sites, the NPCN-1 when measuring at 1 M H2SO4 electrolyte can
also obtain a large specific capacitance of 252 F g
1 at 0.5 A g
1
(Figs. S3a and 3b).
The exploration of the application of NPCN-1 as both positive
and negative electrodes for practice is conducted by an assembled
symmetric supercapacitor device in 6 M KOH electrolyte. The CV
curves in Fig. S4a indicate quasi-rectangular curves without
obvious distortion with enlarging the scan rate from 10 to
200 mV s
1, demonstrating an ideal capacitive energy storage
process along with excellent rate capability [67]. As given in
Fig. S4b, the nearly-symmetric triangular GCD curves show the
device can obtain a coulombic efficiency of over 91% at all current
densities, reflecting a good reversibility. Calculated with equation
(2) based on the discharge curves, a specific capacitance of 50 F g
1
at 0.5 A g
1 corresponding 200 F g
1 for a single electrode can be
received by the device, which maintains 70% when tested at
10 A g
1 (Fig. S4c). Obtained from the Bode plot inserted in Figs. S4d
and a characteristic frequency of 0.69 Hz (at the phrase angle
of
45 ) indicates a fast response time of 1.45 s, which can be
ascribed to the fast electron and ion transfer revealed by the small
Rs (1.29 U) and Rct (0.3 U) shown in the Nyquist plot (Fig. S4d). The
cycle stability of the device measured at 10 A g
1 is shown in
Fig. S4e, exhibiting a prominent capacitance retention rate of 92.3%
after 5000 cycles. In Fig. S4f, the Ragone plot indicates that the
NPCN-1 based supercapacitor achieves an energy density of 7 Wh
kg
1 at the power density of 250 W kg
1, which is larger than those
of many carbon-based supercapacitors, such as RH-AC (4.76 Wh
kg
1 at 42 W kg
1) [68], PCN700 (6.5 Wh kg
1 at 80 W kg
1) [69],
PCF (5.9 Wh kg
1 at 70 W kg
1) [70] and M-NPCS (4.4 Wh kg
1 at
103 W kg
1) [71].
The universality of the MPC strategy is confirmed by using
0.005 M ferric chloride solution to substitute for the water that
disperses the g-C3N4 while keeping other experiment processes
unchangeable. The obtained product is labeled as NPCN-1-Fe,
which maintains the nanosheets structure well, as shown in Fig. 6a.
The specific surface area of the NPCN-1-Fe is 469.4 m2 g
1, deduced
from the nitrogen adsorptionedesorption isotherms (Fig. S5). The
surface elements on the NPCN-1-Fe revealed by the XPS survey
spectrum in Fig. 6b comprise of C, N, O and Fe, with the atom
percentages of 80.3%, 12.8%, 5.7% and 1.3%, respectively, demon-
strating the effectively triply-doped O, N and Fe on the NPCN-1-Fe.
Shown in the Fe 2p core-level spectrum (inset of Fig. 6b), the spin
energy separation between Fe 2p1/2 (724.2 eV) and Fe 2p3/2
(710.6 eV) is 13.6 eV, in accordance with that for Fe2O3 [72]. Due to
the introduction of Fe2O3, the oxidation peaks (~-0.62 and
0.78 V)
and reduction peaks (~-0.89 and
1.02 V) can be easily found from
the CV curves of the NPCN-1-Fe in Fig. 6c, indicative of the further
contribution of the pseudo-capacitance. In Fig. 6d, the specific
capacitance of NPCN-1-Fe at 0.5 A g
1 is calculated to be 279 F g
1
(0.59 F m
2), 71.3% of which can be retained after the current
density enlarging to 30 A g
1, implying the effective active sites, fast
electron and ion transfer in NPCN-1-Fe after N, O and Fe2O3 tri-
doping by MPC.
8
Journal of Alloys and Compounds 860 (2021) 157898
3.3. Characterization of the microwave absorption performances of
the samples
In general, the real part of the permittivity ε0 and permeability m0
stands for the storage capability of EM energy in the material, and
the imaginary part of the permittivity ε00 and permeability m00 re-
flects the energy loss or dissipation [73,74]. As shown in Fig. 7a and
b, the e0 and e00 for the NPCN-1 at 2 GHz are 9.5 and 3.0, respectively,
while those for the GCB are 5.0 and 0.3. The higher complex
permittivity of the NPCN-1 than that of the GCB is attributed to the
high conduction loss and polarization loss. Moreover, the NPCN-1
compared with GCB possesses a higher tande in the frequency
range of 2e18 GHz, shown in Fig. 7c, which can be ascribed to its
high electrical conductivity and surface charge originating from
high N doping amounts [47]. To evaluate the EM attenuation
capability of the samples, the attenuation constant (a) is deduced
according to the following equation [75].where c and f denote the
velocity of light and the frequency of EM waves, respectively. From
the results displayed in Fig. 7d, it can be obtained that the NPCN-1
possesses a larger attenuation constant a than the GCB throughout
the frequency range measured, obtaining prominent microwave
attenuation ability.
Shown in Fig. 8 are the reflection loss maps for the GCB and
NPCN-1 samples at different thicknesses in the frequency range of
2e18 GHz. The GCB in Fig. 8a exhibits a weak absorption peak of RL
value of
18.6 dB at 13.6 GHz with a thickness of 2.9 mm, and the
effective absorption bandwidth (corresponding to the RL lower
than
10 dB) is 0.88 GHz. By contrast, the NPCN-1 in Fig. 8b with
the thickness of only 2.3 mm displays a broad effective absorption
bandwidth of 6.64 GHz along with a strong RL of
44.5 dB at
13.52 GHz, which indicates an excellent microwave absorption
(MA) performance, in line with the results in Fig. S6a. The com-
parison of MA performances between the NPCN-1 and the carbon-
based composites reported in recent years is listed in Table S2, in
which the thinner matching thickness combined with broadband
and strong absorption for the NPCN-1 make it a very promising
material candidate in future MA field.
In addition, the impedance matching (|Zin/Z0|) characteristic at
the sample surface is a vital factor to evaluate the MA performance,
which can be calculated by the following equation [76,77].
rffiffiffiffiffi  
Zin mr 2pfd pffiffiffiffiffiffiffiffiffi
¼ tanh j mr εr (10)
Z0 εr c
The closer the value of |Zin/Z0| is to 1, the better the impedance
matching [78]. Compared with that of the GCB, the |Zin/Z0| value of
the NPCN-1 as recorded in Fig. S6b was closer to 1 in the frequency
range of 9e16 GHz, suggesting the better impedance matching
properties. The maximum absorption peak (
44.5 dB) of NPCN-1 is
at 13.52 GHz (Fig. S6a), corresponding to the |Zin/Z0| value of 1,
which indicates EM waves are completely incident into the
absorbing materials to enhance the EM absorbing performance.
Based on the discussion above, the possible EM wave absorption
mechanisms (Fig. 8c) of the NPCN-1 with prominent surface char-
acteristics can be understood as follows: Firstly, the abundant solid-
void interfaces as revealed by the SEM offer a way of interfacial
polarization relaxation loss to transform the electromagnetic en-
ergy into heat energy. Secondly, the optimized porous structure in
the NPCN-1 is helpful for multiple scattering and reflection, which
prolongs the diffusion path, as confirmed by the positive correla-
tion of the maximum reflection loss with pore volume in Fig. S7 and
Table S3. Thirdly, the NPCN-1 possesses the higher conductivity,
making free electrons easy to transport under the action of the
electromagnetic field and thus producing more conduction loss.
Finally, the dipolar polarization originated from the richly-doped
S. Liu, Y. Peng, Q. Han et al. Journal of Alloys and Compounds 860 (2021) 157898

Fig. 6. (a) SEM image, (b) XPS survey spectrum inserting with Fe 2p core-level spectrum, (c) CV and (d) GCD curves of NPCN-1-Fe.

Fig. 7. MA performances evaluation: (a) real part ε0 and (b) imaginary part ε00 of the permittivity, (c) dielectric loss tangent (de) and (d) attenuation constant of the GCB and NPCN-1
in the frequency range of 2e18 GHz.
pffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2pf
a¼ ðm}ε}
m0 ε0 Þ þ ðm}ε}
m0 ε0 Þ2 þ ðm0 ε} þ m}ε0 Þ2 (9)
c

9
S. Liu, Y. Peng, Q. Han et al.
Fig. 8. Reflection loss maps for the GCB (a) and NPCN-1 (b) at different thicknesses in the frequency range of 2e18 GHz; (c) illustration of the microwave absorption mechanisms of
the NPCN-1.
elements such as N and O is favorable for the improved microwave
absorption performance.
Moreover, after decoration of Fe2O3, the effective absorption
bandwidth can be further improved by the NPCN-1-Fe, delivering
7.04 GHz under the thickness of 3.1 mm (Fig. S8). The reason that
effective bandwidth is increased in the case of NPCN-1-Fe is
attributed to the introduction of magnetic properties. As shown in
Figs. S9a and 9b, due to decorating with Fe2O3, the NPCN-1-Fe
composite shows an obvious increment in complex permeability
compared with the NPCN-1 where the real part (m0 ) and imaginary
part (m00 ) of the complex permeability are almost close to 1 and 0.
Additionally, it can be deduced from Fig. S9c that the NPCN-1-Fe
sample compared with the NPCN-1 maintains a |Zin/Z0| value
close to 1 over a wider frequency range, which demonstrates a
better impedance matching. These results reveal that an extra
magnetic property dominated by the NPCN-1-Fe contributes to
increase magnetic loss and further optimize the impedance
matching properties, which result in the increased effective ab-
sorption bandwidth in the NPCN-1-Fe. Thus, the current strategy
displayed by us provides the potential to prepare other materials
requiring simple and precise control of heteroatoms and porosities
to obtain prominent energy storage and microwave absorption
performance.
4. Conclusion
In summary, an effective melting-pressing-carbonization (MPC)
strategy has been successfully demonstrated to simultaneously
integrate rich N- and O-containing groups and ion-matched pores
on the interconnected carbon nanosheets to improve energy stor-
age and microwave absorption. The carbon nanosheets with the N,
10
Journal of Alloys and Compounds 860 (2021) 157898
O doping and porosity can be regulated via easily altering the used
amount of g-C3N4 precursor during the MPC process. In the opti-
mized carbon nanosheet (NPCN-1), abundant N contents of 14.1%
and concentrated ions size on 0.7 nm are found to accelerate
electron and ions transport, and thus to contribute to both
improved electric double layer capacitance and pesudocapacitance.
At 0.5 A g
1, the specific capacitance reaches up to 245 F g
1,
maintaining 70.6% after the current density enlarging to 20 A g
1,
even comparable to the activated carbons using corrosive activa-
tors. Furthermore, these unique surface characteristics and porous
architecture in NPCN-1 can also enable it to be an exceptional mi-
crowave absorption material, displaying a wide bandwidth of
6.64 GHz at a low filler loading of 20% and strong reflection loss (RL)
of
44.5 dB, superior to most of carbon-based microwave absor-
bents. Due to the multiple controls of active sites with the MPC
method, these performances can be further improved by doping
trace of Fe2O3. The current work paves the way to engineer 2D
carbon nanosheets with high nitrogen doping and ions-matched
porosity in large-scale, which can be extended to other fields that
require the material with novel design on surface characteristics
and porosity.
5. Notes
The authors declare no competing financial interest.
Author contribution
Shaobo Liu and Yuhui Peng contributed to this work equally.
S. Liu, Y. Peng, Q. Han et al.
CRediT authorship contribution statement
Shaobo Liu: and. Yuhui Peng: Writing - original draft, prepared
the materials and drafted the manuscript. Qiang Han: Formal
analysis, and. Chenggang Yang: Formal analysis, helped conduct
the structure analyses and electrochemical performance tests of the
samples. Lianwen Deng: provided important advices and conve-
nient tests. Jianfei Zhou: analyzed some experimental results
about microwave absorption. All authors had read and approved
the final manuscript. Xiaoliang Liu: Writing - original draft,
Writing - review & editing, designed the work and guided the
writing.
Declaration of competing interest
We declare that no conflict of interest exits in the submission of
this manuscript.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 51673217) and Project of
Innovation-Driven Plan in Central South University (Grant No.
502221904).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2020.157898.
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