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High-Volumetric Supercapacitor Performance of Ordered

Mesoporous Carbon Electrodes Enabled by the Faradaic-Active
Nitrogen Doping and Decrease of Microporosity
Mingjiang Xie,* Han Meng, Jian Chen, Yan Zhang, Cheng Du, Liu Wan,* and Yichang Chen*
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ABSTRACT: Introducing electroactive nitrogen functionalities and decreasing microporosity are favorable for increasing the bulk
density and thus beneficial for enhancing the volumetric performance of supercapacitors (SCs) that are based on ordered
mesoporous carbon (OMC). Herein, a universal method of graphitic carbon nitride (g-C3N4)-mediated self-assembly of phenolic
resin and F127 surfactant was developed to prepare nitrogen-doped ordered mesoporous carbon (NOMC), in which g-C3N4 mainly
serves as the nitrogen source to functionalize the surface of the mesoporous carbon. Doped with electroactive functionalities, the
NOMC shows low microporosity and highly exposed external surfaces. The nitrogen mainly exists as pyridinic N (N-6), pyrrolic N
(N-5), and pyridinic nitrogen oxide (N-O), showing a high content of up to 24.1 atom %. With the maintenance of ordered
mesoporosity, ordered channels are observed. Benefited from the large amount of the accessible electrochemically active nitrogen
species, volumetric SC performance superior to those of some recently reported nanocarbon electrodes could be achieved, including
a large capacitance of 420 F/cm3 (382 F/g equivalent) at 0.5 A/g and maintaining 258 F/cm3 at 20 A/g, an excellent rate capability
of 61.4% (vs 27.1% of OMC973), and an excellent energy density of 29.8 W h/L at 990 W/L, implying promising candidacy for
portable energy storage devices. Moreover, the fabricated carbon material with ordered mesoporosity and rich nitrogen
functionalities may find wide application in areas such as sorption and catalysis.
KEYWORDS: g-C3N4, nitrogen functionalities, ordered mesoporous carbon, aqueous supercapacitor, high volumetric capacitance

1. INTRODUCTION shortcomings of carbon-based SCs lie in the low energy

Due to charming features such as superlong cycle life and density resulted from low storing capacity. The storing
mechanism of carbon materials shows that their capacity is
ultrahigh power density, supercapacitors (SCs), a member of
highly related to the effectiveness of the surface area, namely,
the energy storage devices,1−4 are considered more promising
the ion-accessible surface area rather than the physical specific
than secondary batteries.5,6 Various electrode materials
surface area. Because of physical specific surface area, channel
including transition metal oxides/hydroxides/nitrides/phos-
surfaces that are inaccessible to ions are observed. To increase
phide/sulfides,7−11 electroactive polymers,12 and carbons13,14
the ion-accessible surface, open structures with decreased
have been developed for the manufacture of SCs. The first two
types are usually called pseudocapacitive materials because
they store energy by reversible faradaic reactions with the Received: November 24, 2020
electrolyte. As for the carbon-based SCs, they mainly store Accepted: January 27, 2021
energy by electric double layer capacitance (EDLC) via Published: February 9, 2021
adsorption of electrolyte ions on the electrode interior surface,
thus enabling power density and ultralong cycle life superior to
those of pseudocapacitive materials. However, the major

© 2021 American Chemical Society https://dx.doi.org/10.1021/acsaem.0c02948

1840 ACS Appl. Energy Mater. 2021, 4, 1840−1850
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Figure 1. Schematic diagram on the fabrication of NOMC.
diffusion resistance and shortened ion transportation distance
have been explored. Recently, advanced carbon-based
electrode materials were developed to obtain a high-
gravimetric capacity by designing a hierarchical carbon with
an accessible porosity and rich redox-active heteroatomic
functionalities (e.g., N, O, P, B).15−22 As a result, the
gravimetric capacity of carbon materials was enhanced to a
high level. Nonetheless, despite the advancement, the
volumetric capacity remains unsatisfactory (usually below
200 F/cm3).23 This is because the increase of microporosity
would generally lead to large specific surface areas and total
pore volumes, resulting in the decrease of bulk density and
volumetric capacitance. For portable devices, a low volumetric
capacitance is disadvantageous. Thus, a carbon-based electrode
material with a relatively low porosity but high in both
gravimetric and volumetric capacitance is highly coveted. In
this regard, developing a nanocarbon material of low porosity
and richly endowed with redox-active functionalities would be
an effective strategy.
Ordered mesoporous carbons (OMCs) are promising hosts
for energy storage.24,25 With long-arranged mesopores and
relatively large surface area, they provide vast channels for fast
EDLC formation. Actually, the OMC-based SCs, particularly
for those based on soft-templated OMCs, usually perform
poorly. Due to the large dimension and high microporosity,
they are limited in ion diffusion, thus resulting in low
capacity.14 To enhance the energy storage level of OMC-
based electrodes, a carbon material that is low in microporosity
and rich in electrochemically active functionalities is perfect.
However, the introduction of a high level of nitrogen species
(over 10 atom %) on the skeleton of OMCs would severely
damage the ordered mesoporosity. Thus, it is a great challenge
to synthesize OMC materials suitable for energy storage.
In the present study, a nitrogen-doped OMC (denoted
herein as NOMC) with an ultrahigh nitrogen content of 24.1
atom % was fabricated by employing graphitic carbon nitride
(g-C3N4) as the nitrogen source to functionalize the surface of
mesoporous carbon (Figure 1). The method involves the self-
assembly of phenolic resin (carbon source) and F127
surfactant (template) mediated by g-C3N4, and the nitrogen
species are mainly pyridinic N (N-6), pyrrolic N (N-5), and
pyridinic nitrogen oxide (N-O). Compared with the OMC
counterpart, not only ordered mesoporosity but also decrease
in microporosity from 66.5 to 12.9% was observed. As the
electrode for SCs, the NOMC achieves a large volumetric
capacitance of 420 F/cm3, displaying an excellent rate
capability of 61.4% and a superior energy density of 29.8 W
h/L at 990 W/L, which is better than that of OMC973 (14.8
W h/L at 945 W/L).
2. EXPERIMENTAL SECTION
2.1. Synthesis. Typically, 0.94 g of phenol (0.01 mol), 3.0 mL of
formaldehyde (37%, 3.0 mol), and 0.01 g of NaOH were dissolved in
10.0 mL of distilled water under vigorous stirring for 6 h to form a
homogeneous precursor solution. Then, 1.5 g of F127 surfactant was
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dissolved in 20 mL of 0.2 M HCl to form a homogeneous template
solution. Then, a designated amount of g-C3N4 (phenol/g-C3N4
molar ratio = 1:3, 1:4, and 1:5) was introduced to the template
solution and the mixture was stirred for 72 h to get a precipitate of
phenolic resin-F127 and g-C3N4. The obtained precipitate was filtered
out and dried at 373 K for 12 h with the purpose of getting a rigid
mesophase. The derived substance was carbonized at 973 K to
remove the template. The so-obtained OMC that was doped with a
high content of nitrogen is herein denoted as NOMC973-C1Nx (x =
3, 4, and 5). For comparison, a pure OMC was also fabricated by the
above method without using g-C3N4 and is herein denoted as
OMC973.
2.2. Characterization. The crystallinity of the products was
analyzed by wide-angle X-ray diffraction (XRD, XRD-6100) and
Raman spectrometry (Horiba Scientific LabRAM HR Evolution).
Scanning electron microscopy (SEM, Carl Zeiss Sigma 300) and
transmission electron microscopy (TEM, JEOL 2100F) were adopted
to measure the microstructure and morphology. The ordered
mesoporous structure was confirmed by small-angle XRD (SAXRD)
on a Rigaku Ultima IV. The textual parameters were obtained by
nitrogen sorption isotherms (Micromeritics ASAP3020) at liquid
nitrogen temperature, and the surface areas were calculated by the
Brunauer−Emmett−Teller method and the pore size distribution was
calculated by the density functional theory method. The surface
component and the heteroatomic species were identified by X-ray
photoelectron spectrometry (XPS, Thermo ESCALAB 250XI). The
bulk density (ρ, g/cm3) of the active material in the electrode was
calculated by eq 126
ρ=
1
Vt + ( ) 1
ρT (1)
where Vt is the total pore volume (cm3/g) and ρT is the true density
of carbon (2.0 g/cm3).
2.3. SC Tests. The SC performances of the derived products were
tested in three- and two-electrode configurations on a CHI660E
workstation adopting the cyclic voltammetry (CV), galvanostatic
charge/discharge curves (GCD), and AC impedance techniques. The
electrode with a mass loading of about 1.0 g/cm3 was prepared by
coating a slurry mixture containing 75 wt% of active materials, 20 wt
% of conductive carbon, and 5 wt % of PTFE binder onto a steel mesh
(300 mesh), followed by pressing at 10 MPa. For the three-electrode
configuration, the fabricated electrode was used as the working
electrode, Ag/AgCl was employed as the reference electrode, a Pt foil
was adopted as the counter electrode, and 1.0 M H2SO4 was utilized
as the electrolyte. The gravimetric capacitance was calculated by
referring to the GCD curves according to the formula Cg = IΔt/mΔV,
where Cg (F/g) denotes the specific capacitance, I is the charge/
discharge current, m is the weight of the active materials, and ΔV is
the discharge potential window. The two-electrode cell was
constructed by immersing the two working electrodes with the
same active material in the 1.0 M Na2SO4 electrolyte. The gravimetric
capacitance (Cg) of the cell was calculated from the GCD plots
I Δt
according to the formula Cg = 2 × mΔV (F/g), where I is the current
(A), m is the mass of the active material in a single electrode (g), t is
the discharge time (s), and ΔV is the discharge voltage window (V).
The energy densities and power densities of the cells were calculated
1 1
according to the formulas Eg = 8 × 3.6 × CgV 2 (W h/kg) and Pg =
Eg/t (W/kg), respectively, where Cg (F/g) is the capacitance of the
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Figure 2. SEM images of (a) OMC973, (b) NOMC973-C1N3, (c) NOMC973-C1N4, and (d) NOMC973-C1N5.
Figure 3. TEM (a−c) and high-resolution TEM images (d) of NOMC973-C1N4.
single electrode, V (V) is the working voltage of the cell, and t (s) is
the discharge time. The volumetric capacitances of the electrodes
were calculated by the formula Cv = Cg·ρm, where Cv (F/cm3) is the
volumetric capacitance of the electrode, Cg (F/g) is the gravimetric
capacitance of the electrode, and ρm is the bulk density calculated by
eq 1. Accordingly, the volumetric energy density and power density
were calculated by Ev = Eg·ρm and Pv = Pg·ρm, respectively.
3. RESULTS AND DISCUSSION
3.1. Morphology and Microstructure Analysis. The
success of the developed approach for the fabrication of OMC
by the aqueous self-assembly of phenol and formaldehyde with
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a surfactant template was verified by the transmission electron
micrographs displayed in the Supporting Information. Figure
S1a,b shows the morphology of OMC973. The TEM images
viewed along different directions display an ordered meso-
porous structure, verifying the success of constructing OMC by
the aqueous self-assembly method. The morphology of
OMC973 was further observed by SEM (Figure 2a), revealing
the formation of a bulk morphology attributable to the 3D-
cross-linking characteristics of phenolic resin which enables the
three-dimensional growth. The morphologies of the g-C3N4-
mediated products are shown in Figure 2b−d, which illustrates
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Figure 4. (a) XRD patterns, (b) Raman spectra, (c) nitrogen sorption isotherms, and (d) the corresponding pore size distribution curves of
OMC973 and NOMC973-C1Nx.
the gradual establishment of a hierarchical structure consisting
of macropores and mesopores with the increase of phenol/g-
C3N4 molar ratio from 1:3 to 1:5. Upon carbonization, g-C3N4
decomposed and generated nitrogen-containing gases that
could in situ nitride the skeleton and simultaneously etch the
surface of OMC973, resulting in functionalization and the
formation of hierarchical structures. The TEM images of
NOMC973-C1Nx at different magnifications are shown in
Figures S1 and3. The TEM images of NOMC973-C1N3 in
Figure S1c,d exhibit ordered mesoporosity, implying main-
tenance of the ordered structure at the phenol/g-C3N4 molar
ratio of 1:3. When the phenol/g-C3N4 molar ratio is 1:4, the
TEM images (Figure 3a−c) of NOMC973-C1N4 also show
ordered mesoporosity, but cavities are observed, which further
confirm the existence of a hierarchical porous structure. It is
deduced that with the phenol/g-C3N4 molar ratio beyond 1:3,
the removal of g-C3N4 during carbonization would leave
cavities in the skeleton of the derived carbon. The high-
resolution transmission electron micrograph of NOMC973-
C1N4 in Figure 3d shows patches of disordered fringes,
indicating the existence of graphite nanocrystallites. Figure
S1e,f shows the TEM images of NOMC973-C1N5 at different
magnifications, which display disordered porous hierarchy with
localized foam-like structures (Figure S1f). The TEM results of
NOMC973-C1N5 imply that the excess usage of g-C3N4
would not result in the mesoporous structure. This is because
the generation of a large amount of nitrogen-containing gases
during g-C3N4 carbonization would result in overetching of the
derived mesostructure. Based on the results of this systematic
investigation, it is considered that the phenol/g-C3N4 molar
ratio for the optimal formation of the ordered mesostructure is
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1:4. The ordered mesoporous structure of the derived NOMCs
was further confirmed by SAXRD. As shown in Figure S2, the
SAXRD patterns of OMC973, NOMC973-C1N3, and
NOMC973-C1N4 all show a diffraction peak at around 0.6°,
ascribed to the (100) diffraction of an ordered structure. As
compared with OMC973, the SAXRD peaks of NOMC973-
C1N3 and NOMC973-C1N4 gradually turn weak, implying
that the ordered mesoporosity would be destroyed as the usage
of g-C3N4 increases. The SAXRD pattern of NOMC973-C1N5
shows no diffraction peak, suggesting the loss of the ordered
mesoporous structure. Being consistent with the TEM results,
the results of SAXRD further verified that the phenol/g-C3N4
molar ratio for the optimal formation of the ordered
mesostructure is 1:4.
3.2. Graphitization Degree and Textural Structure
Analysis. Wide-angle XRD and Raman spectroscopy were
adopted to examine the graphitization degree of the OMC
products. The XRD patterns of the products all exhibit two
wide diffraction peaks at around 26 and 44° (Figure 4a), which
could be indexed to (002) and (101) diffraction of graphite,
suggesting the existence of graphite nanocrystallites, in
agreement with the high-resolution TEM (HRTEM) results.
The intensity of the two peaks over the NOMC973-C1Nx
samples is lower than that of OMC973, indicating the decrease
of graphitization level with the introduction of nitrogen
functionalities. Raman spectra of the samples in Figure 4b all
exhibit two peaks at 1350 and 1590 cm−1, which are ascribable
to the D- and G-band of graphite,27 further confirming the
existence of graphite nanocrystallites, in agreement with the
XRD and HRTEM results. The G- to D-band intensity ratio
(IG/ID) is usually adopted to measure the graphitic degree of
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Table 1. Textural Parameters of the Derived Products Measured by Nitrogen Sorption

sample Stotal (m2/g) Smicro (m2/g) Vmicro (cm3/g) Vtotal (cm3/g) Sexter (m2/g) Smicro/Stotal(%)
OMC973 489 325 0.13 0.45 164 66.5
NOMC973-C1N3 234 72 0.03 0.37 162 30.8
NOMC973-C1N4 272 35 0.06 0.41 237 12.9
NOMC973-C1N5 321 96 0.08 0.56 225 29.9

Figure 5. Full-scan XPS spectra (a) of the resultant products and core-level N 1s XPS spectra of (b) NOMC973-C1N3, (c) NOMC973-C1N4, and
(d) NOMC973-C1N5.

carbon materials. As shown in Figure 4b, the IG/ID ratio for
OMC973, NOMC973-C1N3, NOMC973-C1N4, and
NOMC973-C1N5 is 1.07, 1.02, 1.01, and 0.99, respectively.
The gradual decrease of IG/ID value further verifies the
decrease of the graphitic level with the increase of nitrogen
functionalities. The nitrogen sorption isotherms (Figure 4c) of
the four samples all show IV-type isotherms with a hysteresis
loop at relative pressures of 0.6−0.9, suggesting the existence
of a mesoporous structure. The pore size distribution plots of
the samples in Figure 4d show a mean size distribution of ca.
2.1 nm, confirming successful construction of the mesoporous
structure. The textual properties of OMC973, NOMC973-
C1N3, NOMC973-C1N4, and NOMC973-C1N5 are com-
piled in Table 1. For OMC973, the total surface area is 489
m2/g, of which 325 m2/g is a contribution from micropores.
With the introduction of nitrogen species, an obvious decrease
of specific surface area was observed. The total surface areas of
NOMC973-C1N3, NOMC973-C1N4, and NOMC973-C1N5
are 234, 272, and 321 m2/g, respectively. The ratio of the
microporous surface area to total surface area (Smicro/Stotal) was
calculated to scale the microporosity of the samples. The
microporosity of OMC973 is 66.5%, whereas those of
NOMC973-C1N3, NOMC973-C1N4, and NOMC973-
C1N5 are 30.8, 12.9, and 29.9%. The sharp decrease of the
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total surface area after nitrogen introduction can be ascribed to
the reduction of microporosity. The sharp reduction of
microporosity can be related to the etching intensity on the
micropores by the generated nitrogen-containing gases during
carbonization. This is testified by the sharp decrease of the
microporous surface from 325 m2/g of OMC973 to 72 m2/g of
NOMC973-C1N3, 35 m2/g of NOMC973-C1N4, and 96 m2/
g of NOMC973-C1N5.
The above SAXRD, TEM, and nitrogen sorption results
confirm the success in constructing OMC by the developed
strategy. With NaOH as the catalyst, the starting materials of
phenol and formaldehyde could spontaneously polymerize to
form a soluble phenolic resin. The formed resin could assemble
with the F127 micelle by hydrogen bond and electrostatic
interaction under acidic conditions to form a mesophase of
F127@resin. With further polymerization of phenolic resin
under acidic conditions, a coprecipitate of g-C3N4@F127@
resin was obtained. Due to the thermosetting characteristic of
the resin and the high-temperature decomposition property of
the adopted g-C3N4, OMCs with rich nitrogen functionalities
were successfully fabricated.
3.3. Surface Chemistry Analysis. The surface chemistry
of the derived carbons is critical for their application in fields
such as sorption, catalysis, and energy storage. To disclose the
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Table 2. Surface Composition of OMC973 and NOMC973-C1Nxs Analyzed by XPS
sample C (atom %) N (atom %) O (atom %) pyridinic N (atom %)
OMC973 95.4 0 4.6
NOMC973-C1N3 77.6 18.3 4.1
NOMC973-C1N4 71.9 24.1 4.0
NOMC973-C1N5 72.3 23.8 3.9
Figure 6. Three-electrode configuration tested SC performances of the resultant products in the 1.0 M H2SO4 electrolyte, (a) CV plots of the
NOMC973-C1N4 electrode, (b) GCD curves of the NOMC973-C1N4 electrode, (c) specific gravimetric capacitances of the four electrodes, and
(d) specific volumetric capacitances of the four electrodes.
surface chemical nature of the derived carbons, XPS was
conducted. Figure 5a displays the full-scan spectra of the three
nitrogen-doped carbons, which all show peaks of C, N, and O.
To identify the surface nitrogen species, the N 1s profiles were
deconvoluted. Interestingly, as shown in Figure 5b−d, the N 1s
profiles show components at ca. 398, 400, and 402 eV
assignable to pyridinic N (N-6), pyrrolic N (N-5), and
oxidized N (N-O), respectively.28 It was reported that the
three nitrogen species are all electrochemically active, and their
presence is beneficial to the enhancement of the energy storage
level. The detailed contents of the components are listed in
Table 2. One can observe that the change of the surface oxygen
content across the four samples is not significant, varying from
3.9 to 4.6 atom %, indicative of high stability of residual
oxygen. The nitrogen contents of the three NOMC samples
are 18.3, 24.1, and 23.8 atom % for NOMC973-C1N3,
NOMC973-C1N4, and NOMC973-C1N5, respectively. The
lower nitrogen content of NOMC973-C1N5 in comparison
with that of NOMC973-C1N4 suggests that at the phenol/g-
C3N4 molar ratio beyond 1:4, there is a slight decrease of
nitrogen functionalities, possibly caused by the slight loss of
residual oxygen. In the deconvoluted C 1s profile of OMC973
(Figure S3a), there are three fitted peaks at ca. 284, 285, and
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pyrrolic N (atom %) pyridinic oxide (atom %)
0 0 0
8.6 8.1 1.6
11.9 8.6 3.6
10.7 9.1 3.6
289 eV, corresponding to −CC− (sp2), −C−C−/−C−H
(sp3), and −CO (carbonyl), respectively. After the
introduction of nitrogen functionalities, the C 1s spectra
(Figure S3b−d) of NOMC samples all exhibit four fitted peaks
at ca. 284, 285, 287, and 289 eV, ascribable to −CC− (sp2),
−C−C−/−C−H (sp3), −CN−, and −CO (carbonyl),
respectively. Compared to OMC973, the newly emerged peak
at 287 eV of the −CN− species further confirms the
successful modification of the carbon skeleton.
3.4. Electrochemical Capacitive Performance Anal-
ysis. The characterization results based on SEM, TEM,
nitrogen sorption, and XPS analyses illustrate that the derived
NOMC973-C1N3 and NOMC973-C1N4 materials own
ordered mesoporosity, hierarchical structures, rich redox-active
nitrogen functionalities, and low microporosity. It is expected
that they should show superior supercapacitive performance,
especially for a volumetric performance. We conducted a
systematical investigation on aqueous SC performance using
the three-electrode and symmetric cell configurations based on
standard CV and GCD techniques. The three-electrode
configuration was adopted to examine the electrochemical
characters of the prepared carbons. Figure S4a shows the CV
plots of the OMC973 electrode at various scan rates, which
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Table 3. SC Performances of the Recently Reported Carbon-Based Electrodes Compared with Our Work
sample Cg (F/g) Cv (F/cm3) electrolyte energy density (W h/L) references
NOMC973-C1N4 385@ 0.5 A/g 420@0.5 A/g 1.0 M H2SO4 29.8 this work
PCS 338@1.0 A/g 254@1.0 A/g 6.0 M KOH 8.8 23
CsCl-T 160@0.1 A/g 50@0.1 A/g 1.0 M LiOH 30
4NPC-800 242@0.5 A/g 306@0.5 A/g 1.0 M H2SO4 15.24 31
PCN-3 242@0.5 A/g 325.7@0.5 A/g 6.0 M KOH 22.1 32
SLC-7 200.2@0.1 A/g 104.5@0.1 A/g 6.0 M KOH 33
NCNFs 362.6@1.0 A/g 302.2@1.0 A/g 6.0 M KOH 36.8 34
BPNOCNF-45 332@1.0 A/g 395@1.0 A/g 6.0 M KOH 21.1 35
DGB 235@1.0 A/g 215@1.0 A/g 6.0 M KOH 36
NMHCSs-0.6-15 240@0.2 A/g 85@0.2 A/g 6.0 M KOH 37
F/N-CNS 266@1.0 A/g 255@1.0 A/g 1.0 M H2SO4 18.8 38

Figure 7. Trasatti analysis results of capacitance vs square root of charge/discharge time for the four carbon electrodes: (a) OMC973; (b)
NOMC973-C1N3; (c) NOMC973-C1N4; and (d) NOMC973-C1N5.

display a rectangular-shaped pattern indicative of typical EDLC
behavior. The GCD curves of the OMC973 electrode in Figure
S4b show a regular triangular-shaped pattern, again verifying
the EDLC character. In sharp contrast, the CV profiles of
electrodes based on NOMC973-C1N3 (Figure S5a),
NOMC973-C1N4 (Figure 6a), and NOMC973-C1N5 (Figure
S6a) collected at various rates all exhibit rectangular-patterned
curves with visible redox peaks at around 0.5 V, suggesting that
the capacity comes from EDLC and faradaic reaction between
the electrochemically active functionalities and electrolyte.29
The GCD plots at various current densities of the NOMC-
based electrodes in Figures S5b, S6b, and 6b all show distorted
triangular-shaped patterns with obvious deviation from the
linear GCD curves at about 0.5 V, further confirming the
coexistence of EDLC and pseudocapacitance. The calculated
gravimetric capacities of the four electrodes are shown in
Figure 6c. Obviously, the specific capacitances of the NOMC
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electrodes are higher than that of OMC973 within the current
density range of 0.5−20 A/g. Maximum capacitance as high as
382 F/g was observed over the NOMC973-C1N4 electrode,
which is roughly 3 times that of OMC973 (113 F/g). At a
large current density of 20 A/g, the capacitance is 235 F/g for
the NOMC973-C1N4 electrode, which is far higher than that
for the OMC973 electrode (30 F/g). From 0.5 to 20 A/g,
capacitance retention for the four electrodes is 61.7% for
NOMC973-C1N3, 61.5% for NOMC973-C1N4, 62.4% for
NOMC973-C1N5, and 26.5% for OMC973. The superior SC
performances of NOMCs to OMC973 can be attributed to the
introduction of a large amount of electroactive nitrogen
functionalities. Moreover, the specific capacitances of NOMCs
obviously increase as the nitrogen content rises since the
introduced nitrogen species are all electrochemically active
ones.
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Figure 8. Symmetric SC performances of the resultant products in the 1.0 M Na2SO4 electrolyte, (a) CV plots of the NOMC973-C1N4 electrode,
(b) GCD curves of the NOMC973-C1N4 electrode, (c) specific capacitances of the four electrodes, and (d) Ragone plots of the resultant carbon-
based electrodes as compared to some recently reported carbon-based electrodes for symmetric SCs.
The Nyquist plots (Figure S7) of the four carbon-based
electrodes indicate that the NOMC electrodes all own a slope
larger than that of OMC973, suggesting improved ion
transportation. With the introduction of rich nitrogen-
containing functionalities and alteration of pore dimension,
there is improved surface wettability and hence enhanced ion
transference. Among the three NOMC electrodes, NOMC973-
C1N5 possesses the biggest slope at low frequency, accounting
for a rate capability of 62.4%, which is the highest among the
three electrodes. Since the derived NOMC materials own low
microporosity and large redox-active nitrogen functionalities,
excellent volumetric SC performance could be expected. The
volumetric capacitances of the NOMC-based electrodes were
calculated according to the formula shown in Figure 6d. At the
six selected current densities in the range of 0.5−20 A/g, the
volumetric capacitances for the four carbon electrodes are 118,
110, 98, 70, 47, and 32 F/cm3 for OMC973; 336, 297, 278,
246, 230, and 208 F/cm3 for NOMC973-C1N3; 420, 352, 319,
293, 274, and 259 F/cm3 for NOMC973-C1N4; and 318, 276,
251, 231, 207, and 199 F/cm3 for NOMC973-C1N4. A
maximum volumetric capacitance of 420 F/cm3 was achieved
over the NOMC973-C1N4 electrode, which is nearly 4 times
that over the OMC973 electrode. For porous carbons, because
of the low intrinsic density and limited capacitance, it is a
challenge to achieve a volumetric capacitance (Cv) higher than
200 F/cm3. Compared to the recently reported carbon-based
electrodes,30−38 the gravimetric and volumetric capacitances
achieved in our work lie in the high level (Table 3). The
superior performance can be attributed to the presence of rich
nitrogen functionalities that provide extra pseudocapacity as
well as the low microporosity that endows a large bulk density
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(0.94−1.15 cm3/g). To identify the pseudocapacitance
originated from the introduced redox-active functionalities,
Trasatti analysis was conducted, in which the capacitance was
plotted against the square root of half-cycle time (Figure 7).
The intersection of the dotted line with the vertical axis
denotes the rate-independent capacitance which indicates that
the EDLC contributions of OMC973, NOMC973-C1N3,
NOMC973-C1N4, and NOMC973-C1N5 are 40, 180, 220,
and 195 F/g, respectively. It means that the pseudocapacitance
contribution of the nitrogen and/or oxygen species is about 73
F/g for OMC973, 113 F/g for NOMC973-C1N3, 165 F/g for
NOMC973-C1N4, and 143 F/g for NOMC973-C1N5.
OMC973 has a higher pseudocapacitance and its EDLC can
be attributed to the more oxygenic functionality content (4.6
atom %) and high microporosity (66.5%). The more oxygenic
functionalities could generate more pseudocapacity, while the
high microporosity would cause poor surface utilization,
resulting in a low electrochemical-active surface. As a result
of the more oxygenic functionalities and low active surface, a
higher pseudocapacitance than its EDLC was obtained. After
nitrogen doping, both the EDLC and pseudocapacity for
NOMCs increase because the introduced nitrogen function-
alities could improve the surface wettability and provide more
extra pseudocapacity.
To evaluate the practical performance for energy storage,
symmetric SCs based on the derived carbons were assembled
and evaluated in 1.0 M Na2SO4 since the aqueous solution of
1.0 M Na2SO4 could realize a high working voltage and thus
favor the enhancement of energy density of the fabricated
device. The CV plots of the four electrodes (Figure S8)
demonstrate that the assembled symmetric SCs can work at
https://dx.doi.org/10.1021/acsaem.0c02948
ACS Appl. Energy Mater. 2021, 4, 1840−1850
ACS Applied Energy Materials
the voltage range of 0−1.8 V. In detail, the CV plots measured
at various rates for OMC973 (Figure S9a), NOMC973-C1N3
(Figure S10a), NOMC973-C1N4 (Figure 8a), and
NOMC973-C1N5 (Figure S11a) all exhibit a typical
rectangular-shaped pattern, indicative of EDLC behavior.
Different from the patterns measured in the three-electrode
configuration, there is no obvious emergence of redox peaks in
the CV plots, plausibly due to the coexistence of the three
types of nitrogen species that results in multiple faradaic
behaviors and hence the near EDLC-like CV curves. The GCD
curves of the electrode based on OMC973 (Figure S9b),
NOMC973-C1N3 (Figure S10b), NOMC973-C1N4 (Figure
8b), and NOMC973-C1N5 (Figure S11b) all display regular
triangular-shaped patterns characteristic of EDLC, which is
consistent with the CV results. The gravimetric capacitances
(Cg) of the symmetric SCs were calculated from the GCD
curves and are shown in Figure 8c. It is clear that the NOMC-
based electrodes achieve a Cg higher than that of the OMC973
electrode at each current density. The maximum Cg is 160 F/g
for NOMC973-C1N3, 241 F/g for NOMC973-C1N4, and
245 F/g for NOMC973-C1N5. The Ragone plots of energy
densities versus power densities of the assembled symmetric
SCs were plotted, as illustrated in Figure 8d. Obviously, among
the four symmetric SCs, the one based on NOMC973-C1N4
achieves volumetric energy densities larger than those of the
others at every power density. The maximum energy density of
the NOMC973-C1N4 electrode is 29.8 W h/L at a power
density of 990 W/L, which is higher than that of the OMC973
electrode (14.8 W h/L@945 W/L), NOMC973-C1N3
electrode (20.7 W h/L@1035 W/L), and NOMC973-C1N5
electrode (25.9 W h/L@846 W/L). Moreover, as depicted in
Figure 8 and Table 3, the storage level of the fabricated
symmetric SCs lies in the high level among the recently
reported carbon electrodes,35,39−42 suggesting great application
potential in energy storage devices. Figure S12 shows the
cycling stability test of the NOMC973-C1N4 electrode. After
10,000 cycles at a current density of 10 A/g, the capacitance
decay is only ca. 3%, indicative of a superior cycling stability.
With ordered mesoporosity and rich nitrogen functionalities,
the derived NOMC materials may also find applications that
are associated with fast mass transference such as sorption,
catalysis, and so on.
4. CONCLUSIONS
In summary, NOMC was fabricated via the g-C3N4-mediated
self-assembly of phenolic resin and F127 surfactant to achieve
an excellent volumetric performance. In our strategy, g-C3N4
mainly serves as the nitrogen source to functionalize the
surface of the mesoporous carbon. Unlike the OMC without
nitrogen doping, the NOMC with electroactive functionalities
shows significantly lower microporosity but higher exposed
external surfaces. With ordered mesoporosity maintained, the
NOMC could own nitrogen content as high as 24.1 atom %.
The nitrogen species are mainly pyridinic N (N-6), pyrrolic N
(N-5), and pyridinic nitrogen oxide (N-O). Endowed with a
large amount of electrochemically active nitrogen species and
ordered channels, the electrode based on NOMC achieves
excellent performance. Under optimal conditions, the volu-
metric capacitance can be as large as 420 F/cm3 (382 F/g
equivalent) (vs 118 F/cm3 of OMC973) at 0.5 A/g and
maintain 258 F/cm3 (235 F/g) at 20 A/g. Furthermore, an
excellent rate capability of 61.4% (vs 27.1% of OMC973) and
an energy density of 29.8 W h/L at 990 W/L could be
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achieved, which is superior to that of OMC973 (14.8 W h/L at
945 W/L) and those of recently reported nanocarbon
electrodes. The developed approach for the introduction of
nitrogen functionalities on a carbon skeleton is simple. The
method may be applicable for the functionalization of
nanostructured carbons as well as for the nitration of metal
oxides to prepare N-doped nanostructures for applications in
areas such as sorption, catalysis, and energy storage.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.0c02948.
TEM images, core-level C 1s XPS spectra, and Nyquist
plots of the derived samples (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Mingjiang Xie − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China; orcid.org/0000-
0002-9966-1911; Email: xiemingjiang@smail.nju.edu.cn
Liu Wan − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China;
Email: wanliuok2006@163.com
Yichang Chen − Research and Design Institute, Wuhan
Institute of Technology, Wuhan 430074, China;
Email: hb_chem@126.com
Authors
Han Meng − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China
Jian Chen − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China
Yan Zhang − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China
Cheng Du − Hubei Key Laboratory for Processing and
Application of Catalytic Materials, Huanggang Normal
University, Huanggang 438000, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.0c02948
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the Natural Science
Foundation of Hubei Province (2019CFB626), the Science
and Technology Innovation Team Plan for the youths in
universities of Hubei Province (T2020021), and the Initial
Research Fund (2042019023) of Huanggang Normal Uni-
versity. The authors thank Prof. C.T. Au for helpful
suggestions.
https://dx.doi.org/10.1021/acsaem.0c02948
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ACS Applied Energy Materials
■
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