Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-017-8381-5

Fabrication of nitrogen-doped porous electrically conductive carbon

aerogel from waste cabbage for supercapacitors and oil/water
separation
Tailong Cai1 · Hanwei Wang1 · Chunde Jin1,2 · Qingfeng Sun1,2   · Yujing Nie1,2

Received: 12 August 2017 / Accepted: 4 December 2017

© Springer Science+Business Media, LLC, part of Springer Nature 2017

Abstract
Nitrogen-doped porous carbon aerogels were prepared by using low-cost and high yield cabbages as carbon source via a
mild method, including hydrothermal, freeze-drying, and carbonization processes. Owing to natural structure and nitro-
gen-containing features, the as-prepared carbon aerogels exhibited hierarchical 3D network porous structure with suitable
nitrogen-doped and high conductivity. With such unique structural characteristics, these carbon aerogels displayed a supe-
rior performance, such as superior capacitance of 291 F g−1 with high large capacitance retention of 96.76% after 10,000
cycles in 6 M KOH electrolyte, as well as high energy density of 97.1 Wh kg−1 with and long cycling stability of 92.87%
after 10,000 cycles in ionic liquid. Moreover, these superoleophilic carbon aerogels exhibited excellent adsorption capacity
and recyclability for various oils and organic solvents. This work fully utilized the advantages of the cabbage leaves derived
porous carbon aerogels as a promising “green” candidate to apply in low-prices and high-performance energy storage devices
and adsorbent materials.

1 Introduction conductivity, chemical stability and low prices properties

Aerogels, as 3D porous solid materials, have been attracted
significant attention because of their intriguing properties,
such as developed porosity, high surface area, low density
and multi-branched network structure [1–3]. Among the
diverse aerogels, biomass-derived carbon aerogels have
become a promising candidate in many applications, includ-
ing adsorbent materials and electrode materials [4, 5]. These
can be ascribed to the biomass-derived carbon aerogels
possess environmental friendliness, reasonable electrical
Electronic supplementary material  The online version of this
article (https://doi.org/10.1007/s10854-017-8381-5) contains
supplementary material, which is available to authorized users.
* Qingfeng Sun
qfsun@zafu.edu.cn
* Yujing Nie
nyj1986@163.com
1 recyclability [22]. Importantly, the demands for high per-
School of Engineering, Zhejiang A & F
University, Hangzhou, Zhejiang Province 311300,
People’s Republic of China
2
Key Laboratory of Wood Science and Technology,
Hangzhou, People’s Republic of China
[6–10].
The pursuit of carbon aerogels derived from different
biomass materials for obtaining high-performance electrode
materials in supercapacitors is becoming an interesting topic
in many research fields. Currently, various biomass materi-
als, such as enteromorpha prolifera [11], pomelo peels [12],
bagasse [13], cantaloupes [14], watermelon [15], cotton
[16], and so on [17–19], are widely explored to synthesize
various carbon aerogels. It is seen that the greatly differences
of the capacitance performance for these biomass-derived
carbon aerogels, indicating the necessity of the structure
design and heteroatoms control of the carbon aerogels as
well as the reasonable choose of the carbon sources. Moreo-
ver, the biomass-derived carbon aerogels also have attracted
extensive attention as adsorbent materials, e.g., magnetite
carbon aerogels from watermelon and iron oxide for absorb-
ing organic pollutants [20], carbon aerogels from eggplant
for adsorbing oil and organic solvents [21], carbon aerogels
from waste pomelo peels with high adsorption capacity and
formance adsorbent materials and the electrode materials of
supercapacitors have many points in common, such as poros-
ity, chemical stability and favorable surface performance.
However, few researchers fully exploit the advantages of one

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biomass-derived carbon aerogel to apply in the energy and
environment fields simultaneously.
Cabbages are widely grown in global with the features of
low prices, rapidly growing and readily availability. Because
of the wastages from production process, transportation
process and commercial package, large amounts of cabbage
leaves with relatively poor appearance would be discarded
before packaging, which provides higher application poten-
tial for their biomass materials. Furthermore, abundant
crude protein inside the cells and the lignocellulose as cell
framework make these cabbages possible as carbon source to
prepared nitrogenous and hierarchical carbon aerogel.
Herein, we report the facile synthesis of carbon aerogels
by using cabbage leaves waste as carbon sources via a simple
freeze-drying and carbonization. This as-prepared porous
carbon aerogels shows unique hierarchical 3D network struc-
ture with natural nitrogen-doped. These features make these
carbon aerogels exhibits a high electrochemical performance
in both aqueous and ionic liquid electrolyte, as well as high
absorption capacity and superior recyclability for various
oils and organic solvents. It implies that cabbage leaves
derived porous carbon aerogels is a promising “green” can-
didate for low-prices and high-performance energy storage
devices and adsorbent materials.
2 Experimental
2.1 Materials
Cabbage was gathered from supermarkets in Hangzhou
City, Zhejiang province, China. Potassium hydroxide
(KOH), polyvinylidene fluoride (PVDF), super-p carbon
black, N-methyl-2-pyrrolidone (NMP) and 1-ethyl-3-meth-
ylimidazolium tetrafluoroborate ­[EMIMBF4] were supplied
from Aladdin Chemistry Co., Ltd and used directly without
further purification. These chemicals were analytical grade.
2.2 Preparation of CCA
50 g cabbage leaves washed by deionized water were cut into
small pieces, which was then pounded to be slurry in the
agate mortar. The obtained slurry was straight decanted into
150 mL autoclaves and heated 12 h at 180 °C. The products
were washed by deionized water for at least three times,
moved into a cylindrical mold, and then put into a cryof-
reezer at − 40 °C for 24 h. After that, the completely frozen
samples were freeze-dried in a Scientz-10N freeze-dryer
(SCIENTZ-18N, Scientz Technology, China) for 48 h (cold
trap temperature ≤ − 55 °C; vacuum pressure ≤ 10 μPa).
Finally, the obtained cylindrical cabbage aerogels were
carbonized at 500, 600 and 700 °C for 4 h at 2 °C min−1
under nitrogen atmosphere, respectively. The corresponding
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Journal of Materials Science: Materials in Electronics
carbonized samples were labelled as CCA-500, CCA-600
and CCA-700, respectively.
2.3 Characterization
Scanning electron microscopy (SEM, FEI, Quanta 200)
and transmission electron microscopy (TEM, FEI, Tec-
nai G20) were used to characterize the prepared cabbage
carbon aerogels (CCAs). X-ray diffraction (XRD) patterns
were collected by XRD technique (Rigaku, D/MAX 2200)
ranging from 10° to 80° by using Cu Kα radiation (40 kv,
30 mA) at a scan rate (2θ) of 4° min−1. Raman spectros-
copy measurements were performed using a Renishaw Via
laser micro-Raman system at an excitation wavelength of
633 nm. The Nitrogen adsorption–desorption isotherms
were used to calculate the specific surface area by the
Brunauer–Emmett–Teller (BET) method. The chemical
compositions were characterized by X-ray photoelectron
spectrometer (ESCALAB 250 XI, Thermofisher Co). The
contact angles (CAs) were measured via contact angle meter
(KRüSS DSA25).
2.4 Electrochemical characterization
The electrochemical experiments of CCA were tested in
the three-electrode system at 25 °C with electrode materi-
als (working electrode), Hg/HgO electrode (reference elec-
trode), Pt foil (1 cm2) (counter electrode), and 6 M KOH
solution (electrolyte), respectively. To prepare working
electrode, the mixture active material powders contain-
ing as-prepared carbon aerogels, super-p, and PVDF at the
weight ratio of 8:1:1 in ethanol solvent were pasted on the
foam nickel (covered about 1 cm2), and then dried at 60 °C
for 24 h. The electrochemical performance of these elec-
trodes were carried out using the CHI660E electrochemical
workstation (Shanghai chenhua Instruments Co.) by cyclic
voltammetry (CV), galvanostatic charge–discharge (GCD)
and electrochemical impedance spectroscopy (EIS) tests.
The potential window is from 0 to 0.8 V. The current den-
sity of 4 A g−1 was applied in cyclic GCD measurements
for over 10,000 cycles. Moreover, EIS tests were performed
by applying the current amplitude of 5 mV, from 0.1 Hz to
100 kHz.
The electrochemical performance of CCA-600 electrodes
in pure ionic liquid of E
­ MIMBF4 were tested by a symmetric
two-electrode cell (CR2025 type cells). Al foil and poly-
propylene microfiber filter film (Celgard2500, 25 μm) were
applied as current collector and separator, respectively. Same
as preparation method of the previous working electrode,
the obtained mixture active material powders were pasted
on the Al foil and dried at 60 °C for 24 h. These products
were assembled to the cell, and then being tested using the
CHI660E electrochemical workstation by CV, GCD and EIS
Journal of Materials Science: Materials in Electronics
tests. The scan rates of CV measurements was varied from
30 mV to 200 mV s−1 ranged from 0 to 3 V. The current den-
sities of GCD measurements were performed in the current
range of 1–20 A g−1. Current loads of 10 A g−1 was chosen
for cyclic GCD measurements for over 10,000 cycles. EIS
measurement of the CCA-600 electrodes was also recorded
by applying the current amplitude of 5 mV, from 0.1 Hz to
100 kHz.
The capacitances in the three-electrode system were cal-
culated according to Eq. (1):
IΔt
C= (1)
mΔV
where C (F g−1), Δt (s), ΔV (V), I (A) and m (g) are the spe-
cific capacitance, discharge time, voltage window, discharge
current and weight of active materials, respectively.
The capacitance of a single electrode in two-electrode
system was calculated by Eq. (2):
2IΔt
CS = (2)
mΔV
where ­CS is the specific capacitance of one electrode, I (A) is
the discharge current, ΔV (V) is the voltage window, and m
(g) represents the weight of active material on one electrode.
The power and energy density of whole supercapacitor
were calculated according to the Eqs. (3) and (4):
1
Et = C (ΔV)2 (3)
4 × 3.6 S
Et
Pt = (4)
t particles. The CCA-600 and CCA-700 in Fig. 2b, c showed
where ­Et (Wh kg−1) and ­Pt (W kg−1) are the specific energy
and power density, respectively. t (h) and ΔV (V) are dis-
charge time and voltage windows, respectively.
2.4.1 EIS analysis
All the Nyquist plots of the CCAs were fitted using an equiv-
alent Randles circuit in Fig. 5f, according to Eq. (5):
1 1
Z = Rs + +
1 1 (5)
j𝜔Cdl + Rct+Wo
j𝜔Cl + Rleak
where Rs is the internal resistance of the electrodes and cell,
­Cdl is the double layer capacitance, Rct is the charge transfer
resistance, ­WO is the Warburg element, ­Cl the mass capaci-
tance at low frequency, and ­Rleak is the leakage resistance at
low frequency. The values of fitting error of the results were
lower than 10%. The specific elements within the Nyquist
spectra were illustrated in Fig. S1. Herein, the Warburg
element ­WO exhibited only the high frequency (45° slope)
behavior and not the transition to low frequency behavior.
This Warburg element was expressed by the Eq. (6):
1
WO = (6)
Q0 (j𝜔)n
where ­Q0 is the modulus of admittance, ω is the pulsating
signal (ω = 2πf), and n is the dispersion index. The obtained
fitting results were displayed in Table S1.
3 Results and discussion
The formation processes of the CCAs through the hydro-
thermal, freeze-drying, and carbonization pathway was
illustrated in Fig. 1. At first, the hydrothermal treatment at
180 °C made the cabbage transform from green to black gel-
atine material, implying the formation of cabbage hydrogel.
After the freeze-drying process, the black cabbage hydrogel
was turned into a brown aerogel (48.3 mg cm−3). Finally, the
cabbage aerogel completely showed a deep black appear-
ance which probably indicated the transformation of CCAs.
The corresponding SEM of the CCAs displayed a series of
broken cabbage cells. In a magnified SEM image, it could
be clearly observed a 3D network structure with abundant
holes in this carbon aerogels which might be responsible
for a relatively high surface area and high-performance for
supercapacitor.
SEM image of CCA-500 in Fig. 2a revealed an inter-
connected and continuous 3D network structure, which was
made up of the plenty of cross-linked irregularity shaped
a similar continuous 3D network structure. Interestingly,
the corresponding magnified SEM images illustrated that
both the number and size of irregularity shaped particles
decreased with the carbonization temperature increased.
These carbon particles aggregated to form hierarchical
pathways and porous structures, which might provide higher
specific surface area in a range of temperature. TEM images
of the CCA-500 in Fig. 2d demonstrated the presence of
irregularity shaped nanoscale spheres that connected to each
other by fiber or a direct connection. Figure 2e displayed
these nanoscale carbon spheres cross-linked with each other
in CCA-600, which formed abundant pore structures. With
carbonization temperature increased from 600 to 700 °C,
these carbon particles gradually converged and formed a
denser structure (Fig. 2f). These unique structures might
provide hierarchical porous and relatively high surface area.
The corresponding HRTEM images showed obviously tur-
bostratic graphitic structures in all samples, revealing high
amorphous structure for these carbon aerogels. In particular,
short-range parallel carbon layer became more obvious with
the temperature increased, implying enhanced graphitization
13

Fig. 1  Schematic illustration of the formation process of CCAs
degree [23]. The EDX mapping based on CCAs demon-
strated the uniform distribution of nitrogen, carbon, and
oxygen elements.
Two broad peaks at 24.7° and 43.8° in all CCA samples
could be identified by XRD technique, which were attrib-
uted to diffraction of disorder carbon (002) and diffraction
of graphitized carbon (101), respectively [24, 25]. It revealed
the partial graphitization structure of CCA. Furthermore, a
shaper and stronger (002) peak at higher carbonization tem-
perature manifested the promotion of graphitization degree.
Raman spectra of CCA were shown in Fig. 3b revealed D
band at 1350 cm−1 and G band at 1585 cm−1, which could
be mainly caused by graphite edge structure and crystalline
graphite, respectively [3]. As the temperature increased, the
D/G band intensities ratio of CCA decreased from 0.92 to
0.76, respectively, indicating a highly disordered structure
for CCA. The nitrogen sorption isotherms of the CCA in
Fig. 3 displayed type-IV sorption isotherm according to
IUPAC classification. A hysteresis loop was clearly observed
at isotherms of all samples, which indicated the existence
of abundant micro/mesopores with an interconnected mul-
tistage channel structure [26]. Table 1 displayed the porous
features of these carbon aerogels. The specific surface area
­(SBTE) of CCA-500, CCA-600, and CCA-700 were 342, 536,
and 446 m2 g−1, and the corresponding pore volume ­(VPore)
were 0.19, 0.32 to 0.26 m3 g−1, respectively. CCA-600 had
a higher specific surface area, implying this sample could
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Journal of Materials Science: Materials in Electronics
provide more ion adsorption sites and ion diffusion pathways
that were beneficial to electrolyte ion transport in CCA-600
electrode material. The pore-size distribution of CCA was
illustrated in Fig. 3d. A wide pore-size distribution with the
pore size ranged from 0.5 to 5 nm appeared in CCA, which
was beneficial to storage of the electrolyte and provide a fast
ion transfer pathway.
The carbon (C), nitrogen (N), and oxygen (O) elements
were observed in survey spectrum of CCA (Fig. 4a). Three
peaks at 283, 398, and 530 eV were ascribed to the C1s,
N1s, and O1s in Fig. 4a, respectively. A narrow trend of the
C1s spectra with the temperature increased was observed
in Fig. S2 that represented improvement of the degree of
graphitization. Table 2 showed the doped-heteroatoms (N
element) decreased with the carbonization temperature.
Before carbonization process, the content of nitrogen for the
cabbage aerogel was measured to be 3.23%. CCA still had
a relatively high nitrogen content from 1.81 to 2.36% after
carbonization process, indicating high retention for nitrogen
element. The high-resolution XPS scans of N1s of CCA was
displayed in Fig. 4b–d. The N1s peak of CCA was com-
posed of oxidized N (N-O), graphitic N (N-Q), pyrrolic N
(N-5), and pyridinic N (N-6), corresponding to 402.8, 401.1,
399.7 and 398.8 eV, respectively [27, 28]. It was seen that
the N-Q could promote the electronic conductivity and the
N-6 could provide more electrons to the π-conjugated sys-
tem of carbon, which were important factors for electrodes
Journal of Materials Science: Materials in Electronics

Fig. 2  SEM images and corresponding magnified SEM images of a CCA-500, b CCA-600 and c CCA-700. TEM and HRTEM images of d
CCA-500, e CCA-600 and f CCA-700. EDX mapping of g C, N and O elements for CCA-600

Table 1  Surface area and porosity of CCA 5 to 200 mV s−1 of the CCA electrodes were shown in
SBET ­(m2 SMicro ­(m2 VPore ­(cm3 DAver (nm)
Fig. 5b and Fig. S3. The CCA-600 still retained a good
­g−1) ­g−1) ­g−1) rectangular shaped voltammetry characteristic with an
highest current densities even at 200 mV s−1, implying an
CCA-500 342 214 0.19 2.2 excellent ions responsitivity and a good electrical double-
CCA-600 536 408 0.32 1.9
layer capacitor behavior. As shown in Fig. 5c, CCA-600
CCA-700 446 352 0.26 2.1 displayed almost linear and symmetrical appearance in
GCD curves, which revealed a low electric resistance for
the CCA-600 (Fig. 5c). The specific capacitances of the
performance [29, 30]. Additionally, Faradaic reaction-based CCA electrodes were calculated by GCD curves in Fig. 5d.
pseudocapacitance were contributed from the N-5 and N-6 At the current density of 0.5 A g −1, the specific capaci-
to increase the capacitance performance by reversible redox tances of CCA-500, CCA-600 and CCA-700 were 238,
reactions [31–33]. 291 and 246 F g−1, respectively. Even at 200 A g−1, the
The electrochemical performances of the CCA-500, CCA-600 and CCA-700 electrodes still maintained high
CCA-600, and CCA-700 electrodes in 6  M KOH were capacitances of 119 and 132 F g−1, respectively. As shown
evaluated in a three-electrode system. As shown in Fig. 5a, in Fig. 5e, the cyclic stability of CCA-500, CCA-600, and
all samples at 100 mV s−1 showed a rectangle shape, indi- CCA-700 electrodes were estimated by GCD curves at
cating a low internal resistance and high ions responsi- 4 A g−1. After 10,000 cycles, the capacitance of that still
tivity for the CCA materials. The CV curves taken from retained 94.25, 96.76 and 97.53%, respectively. These

13
 Journal of Materials Science: Materials in Electronics

Fig. 3  a XRD pattern of the CCA. b Raman spectra of CCA. c Nitrogen sorption isotherms of carbon materials derived from the CCA. d Cor-
responding pore distribution curves of the CCA

Table 2  Chemical composition of cabbage aerogel and CCA materi- based heteroatom-doped porous carbon [39], the CCA-600
als determined by X-ray photoelectron spectroscopy (XPS) also achieved the higher specific capacitances.
XPS (at.%) Electrolyte ion transport and electrochemical behaviors
of the electrode materials were analyzed by using EIS. As
C N O
shown in Fig. 5f, the CCA electrodes revealed a slightly
Cabbage aerogel 43.56 3.23 53.21 slanted line shape in the low-frequency region, indicating
CCA-500 88.31 2.36 9.33 a high capacitive behavior for these electrodes. The shorter
CCA-600 89.56 2.01 8.43 lengths of the CCA-600 and CCA-700 in Warburg region
CCA-700 91.57 1.81 6.62 (~ 45°) revealed lower resistances of electrolyte ions diffu-
sion in comparison to that of the CCA-500. The CCA-600
and CCA-700 also exhibited small semicircle widths, sug-
results could be caused by the synergistic effect of hierar- gesting their low charge transfer resistances [40, 41]. To
chical three-dimensional network porous structure, nitro- further study the interfacial electrochemical behavior of
gen-doped, and high surface area which not only promoted the electrode materials, the Nyquist plots were fitted by a
the hydrophilicity, ion diffusion capacity and conductivity, Randles equivalent circuit in the top of the Fig. 5f. The rela-
but also provided pseudocapacitance and fast ion trans- tionship of the specific elements and Nyquist spectra were
fer pathway [34]. Compared to the previously reported shown in Fig. S1. The corresponding fitting results of the
porous carbon materials (Table 3) such as nitrogen-doped different circuit elements of the CCA electrodes were illus-
graphitic carbon nanocages [31], beehive-like hierarchi- trated in Table S1. The internal resistances (Rs) of 0.782,
cal nanoporous carbon [35], nitrogen-enriched nonporous 0.678 and 0.704 Ω as well as the charge transport resist-
carbon [36], hydrogel-derived heteroatom-doped porous ances (Rct) of 1.175, 0.652 and 0.575 Ω were obtained for
carbon networks [37], porous N-doped carbon [38], chitin CCA-500, CCA-600 and CCA-700, respectively. A lower Rs

13
Journal of Materials Science: Materials in Electronics

Fig. 4  a XPS survey spectra of CCA at 500, 600 and 700 °C and the highresolution N1s spectra of b CCA-500, c CCA-600, d CCA-700

Table 3  Capacitive performance of carbonaceous electrode supercapacitors

Description Specific capacitance Electrolyte Test mode References

Nitrogen-doped graphitic carbon nanocages 248 F g−1 at 1.0 A g−1 6 M KOH Two-electrode [31]
Beehive-like hierarchical nanoporous carbon 250 F g−1 at 1.0 A g−1 6 M KOH Three-electrode [35]
Nitrogen-enriched nonporous carbon 198 F g−1 at 0.05 A g­ −1 6 M KOH Three-electrode [36]
Hydrogel-derived heteroatom-doped porous carbon 214 F g−1 at 0.2 A g−1 6 M KOH Two-electrode [37]
networks
Porous N-doped carbon 108.36 F g−1 at 2 mA c­ m−1 6 M KOH Three-electrode [38]
Chitin based heteroatom-doped porous carbon 255 F g−1 at 1.0 A g−1 6 M KOH Three-electrode [39]
CCA-600 291 F g−1 at 0.5 A g−1 6 M KOH Three-electrode This work

value of CCA-600 could be attributed to an advantageous
synergistic effect between the electron conductivity and the
heteroatoms property [40]. The continuous multi-branched
3D network structure with good graphitization degree for
carbon aerogel could be used as electron transfer pathways,
thus leading to the good electron conductivity of CCA-600
and CCA-700. The low graphitization degree, high oxygen
element content and low surface area of the CCA-500 might
limit they obtain a high conductivity and a large effective
specific surface area, resulting in the enhanced resistances,
low capacitance behavior and poor rate capability of the
electrode. Bode plots was further analyzed to confirm these
points. A transition point at the phase angle of 45° repre-
sented the beginning of the capacitive behavior from the
resistive behavior. The CCA-600 displayed a frequency f0
of 1.467 Hz corresponding to a time constant (τ0 = 1/ f0 ) of
0.682 s, higher than 0.835 s for the CAA-500, but lower than
0.432 s for the CCA-700. This might be attributed to a large

13

Fig. 5  a CV measurements of the CCA at a scan rate of 100 mV s−1
in 6  M KOH aqueous solution. b CV measurements of CCA-600 at
different scan rates from 5 to 200 mV s−1. c GCD curves of CCA-600
at different current densities from 1 to 200 A g−1. d Specific capaci-
tances of the CCA at different current densities. e Cyclic stability of
the CCA electrodes at a charge–discharge current density of 4 A g−1
micropore content and a low graphitization degree of the
CCA-600 compared to the CCA-700. Although the CCA-
700 electrode exhibited a good ion diffusion/transport per-
formance and a high rate capability, a relatively low specific
capacitance at a small current density impeded they access
to a high capacitance at higher current density. These results
indicated that the CCA-600 was a promising electrode mate-
rial in supercapacitor.
To increase the theoretical energy density, using a high
working voltage window in supercapacitor is necessary.
The ionic liquids, as a kind of non-aqueous electrolyte, was
widely used in supercapacitor due to not only it could be
applied in higher voltage, but the non-volatile and low-tox-
icity characteristic. Thus, we employed the ionic liquid of
­EMIMBF4 to increase the working voltage window in this
work. The supercapacitor performance of CCA-600 were
examined in a two-electrode symmetrical coin cells testing
device by using ionic liquid of E ­ MIMBF4 as electrolyte.
Figure 6a showed CV curves of CCA-600 electrode, indi-
cating a good rate capability of the CCA-600 at E ­ MIMBF4
electrolyte due to a large area retention at 200 mV s−1. GCD
curves of the CCA-600 electrode exhibited a good symmetri-
cal shape with a high consistency for CV curves. Compared
to the CCA-600 at 6 M KOH electrolyte, a relatively higher
­IRdrop was observed on GCD curves in Fig. 6b, resulting
13
Journal of Materials Science: Materials in Electronics
for 10,000 cycles. f Nyquist plots for the CCA in the frequency range
from 10,000  Hz to 0.1  Hz. A Randles equivalent circuit displayed
in the top of figure was used to fit the Nyquist spectra. The corre-
sponding resistor and capacitor elements in an equivalent circuit were
related to the specific parts at the magnified spectra in the inset of (f).
g Bode plots of phase angle versus frequency
from the inherent character of the pure ­EMIMBF4. As shown
in Fig. 6c, the specific capacitance of CCA-600 at 1 and
10 A g−1 was 164 and 66 F g−1, respectively. After 10,000
cycles at 10 A g−1, the capacitance performance of CCA-600
electrode retained 92.87% (Fig. 6d). Additionally, energy-
storage property of the electrochemical capacitors were one
of the most crucial factors for supercapacitors performance.
As shown in inset of Fig. 6d, CCA-600 revealed a superior
energy–density from 9.5 to 97.1 Wh kg−1 at power-density
from 18,599 to 1456 W kg−1. Nyquist plots of CCA-600
were shown in Fig. 6e. A same equivalent circuit was used
to fit the Nyquist plot of CCA-600 in E ­ MIMBF4 electro-
lyte. The corresponding fitting results were illustrated in
Table S1. It was clearly observed that the Rs and Rct values
of the whole cell were 3.864 and 21.7 Ω, respectively. These
values were much higher than that of the CCA-600 under the
6 M KOH solution, which was attributed to the high viscos-
ity and large ion sizes of the ­EMIMBF4. These Rs and Rct
values of the CCA-600 were lower than some previously
reported activated carbon material using ionic liquid as elec-
trolyte, such as 4.2 and 24.2 Ω for porous activated carbon
materials [42], about 33 and 110 Ω for activated carbon [43],
and 7.5 and 25.4 Ω for mesoporous activated carbon [44].
These low resistances of the CCA-600 electrode provided
further evidence for the superior electrochemical behavior
Journal of Materials Science: Materials in Electronics
Fig. 6  a CV measurements of CCA-600 at different scan rates from
30 to 200  mV  s−1. b GCD curves of CCA-600 at different current
densities from 1 to 20 A g−1. c Specific capacitances of the CCA-600
at different current densities. d Nyquist plots of the CCA-600 in the
frequency range from 10,000  Hz to 0.1  Hz. The inset in d showed
the magnifed high-frequency region and the resistor and capacitor
of CCA-600. Additionally, the application of the CCA-600
cell in Fig. 6f revealed a high capacitance performance of
this cell.
Figure 7 showed some unique features of these nitrogen-
doped porous carbon aerogels. As shown in Fig. 7a, a high
shining LED light was observed in the closed circuit system
where used carbon aerogels as conductor. The brightness
of this LED light was slightly lower than that of the iron
wire, implying a superior conductivity of this porous car-
bon aerogels. By comparison, the cabbage aerogels did not
have conductivity due to no-shining light. The lipophilicity
of these carbon aerogels were clearly illustrated in Fig. 7b.
The corresponding CAs of pump oil and water were 8.6°
and 76.2°, respectively, which revealed that the CCA-600
had a superoleophilic surface. These characteristics with
porous structure made the CCA-600 become an idea adsorb-
ing material. Figure 7c displayed the burning process of the
oil-saturated carbon aerogels in air for cleaning. Under this
process, the organic solvents was successfully removed,
but the corresponding carbon aerogels survived, indicating
excellent thermostability of these carbon aerogels. Besides,
high absorption capacity of CCA-600 also were observed by
adsorption experiments for many oils and organic solvents,
such as cyclohexane, pump oil, olive oil, acetone, ethanediol,
and ethanol (Fig. 7d). The recycle experiments of CCA-600
elements in a same equivalent circuit related to the specific parts in
the Nyquist plot. e Cyclic stability of the CCA-600 electrodes at a
charge–discharge current density of 10 A g−1 for 10,000 cycles. The
inset showed the Ragone plot of CCA-600 for specific-energy and
power-density at different current densities. f The application of the
CCA-600 cell
via adsorption and burning desorption for ten times were
performed using corresponding solvents in Fig. 7e. It could
be observed that the saturated adsorption capacity decreased
with increasing number of the cycles. The saturated adsorp-
tion capacity of CCA for these solvents became to stabilize
after the first five times. Even after ten cycles of tests, these
materials still retained remarkable adsorption capacity for
these liquids, the value surpassed 60 mg mg−1, indicating
the outstanding reusability of CCA materials.
4 Conclusion
In summary, we employed a mild method to product nitro-
gen doped porous carbon aerogels by using cabbages. These
porous carbon aerogels showed unique interconnected 3D
network structure with high surface area, suitable nitrogen-
doped, and wide pore-size distribution (0.5–5 nm). The
CCA exhibited soupier electrochemical performances with
the maximum capacitor of 291 and 164 F g−1 in different
electrolytes of 6 M KOH and ­EMIMBF4 ionic liquid, respec-
tively. Therefore, these cabbages-derived nitrogen-doped
3D network porous carbon aerogels might have high pos-
sibility to be applied in energy-storage and environmental
protection.
13
 Journal of Materials Science: Materials in Electronics

Fig. 7  a Electrical conductivity

tests of the cabbage aerogels,
the iron wire and the CCA-600.
b The photos of CCA-600 with
water and pump oil drops on the
surface, and the inset showed
the oil and water contact angle
measurements. c Optical images
of the burning of the oil-sat-
urated CCA-600 in air for clean-
ing. d The absorption capacity
of CCA-600 for different oils
and organic solvents (K wt wt−1 
= weightCCA:weightReagent). e
Recyclability of CCA-600 for
these oils and organic solvents
by absorption and burning
desorption process

Acknowledgements  The work was financially supported by Key
Laboratory of Bio-based Material Science & Technology, Northeast
Forestry University, Ministry of Education, SWZCL2016-3, Scien-
tific Research Foundation of Zhejiang A&F University (Grant No.
2014FR077), and the Fund for Innovative Research Team of Forestry
Engineering Discipline (101-206001000713).
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