Carbohydrate Polymers 170 (2017) 107116

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Facile synthesis of cellulose-based carbon with tunable N content for

potential supercapacitor application
Zehong Chen a , Xinwen Peng a , Xiaoting Zhang a , Shuangshuang Jing a , Linxin Zhong a, ,
Runcang Sun a,b,
a
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, PR China
b
Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing, PR China

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

Article history: Producing hierarchical porous N-doped carbon from renewable biomass is an essential and sustainable
Received 31 January 2017 way for future electrochemical energy storage. Herein we cost-efciently synthesized N-doped porous
Received in revised form 1 April 2017 carbon from renewable cellulose by using urea as a low-cost N source, without any activation process.
Accepted 22 April 2017
The as-prepared N-doped porous carbon (N-doped PC) had a hierarchical porous structure with abundant
Available online 25 April 2017
macropores, mesopores and micropores. The doping N resulted in more disordered structure, and the
doping N content in N-doped PC could be easily tunable (0.687.64%). The doping N functionalities could
Keywords:
signicantly improve the supercapacitance of porous carbon, and even a little amount of doping N (e.g.
Cellulose
Lignocellulose
0.68%) could remarkably improve the supercapacitance. The as-prepared N-doped PC with a specic sur-
Porous carbon face area of 471.7 m2 g1 exhibited a high specic capacitance of 193 F g1 and a better rate capability, as
Supercapacitor well as an outstanding cycling stability with a capacitance retention of 107% after 5000 cycles. Moreover,
the N-doped porous carbon had a high energy density of 17.1 W h kg1 at a power density of 400 W kg1 .
2017 Elsevier Ltd. All rights reserved.

1. Introduction
Electrochemical supercapacitors, which can be classied into
electric double-layer capacitor (EDLC) and pseudo-capacitor, are
the most promising devices for energy storage since they exhibit
much higher energy densities than conventional capacitors and
display much better power delivery capabilities than batteries
(Ghosh and Lee, 2012). As compared with pseudo-capacitor, EDLC
shows better cyclic stability, more highly reversible and longer
cycling life, and thus attracts increasing interest (Burke, 2000;
Zhang and Zhao, 2009). Carbon materials, such as porous carbon
(Gamby, Taberna, Simon, Fauvarque, & Chesneau, 2001; Wang and
Kaskel, 2012), carbon aerogel (Li, Wang, Huang, Gamboa, & Sebas-
tian, 2006; Rasines et al., 2015), carbon nanotube (Du and Pan,
2006; Rangom, Tang, & Nazar, 2015), carbon nanosphere (Su et al.,
2011; Yang et al., 2015), graphene (Raccichini, Varzi, Passerini, &
Scrosati, 2015; Vivekchand, Rout, Subrahmanyam, Govindaraj, &
Rao, 2008), and carbon nanober (Li et al., 2011; Yu et al., 2015),
are the irreplaceable blocks for constructing EDLC. Porous carbons
possess high surface area, good electrical conductivity, and well-
Correspondence authors at: State Key Laboratory of Pulp and Paper Engineering,
South China University of Technology, Guangzhou, PR China.
E-mail addresses: lxzhong0611@scut.edu.cn (L. Zhong), ynsun@scut.edu.cn
(R. Sun).
balanced pore size, and are considered to be potential materials for
EDLC. Furthermore, the hierarchical porous structure containing
macropores, mesopores, and micropores is very benecial for ion
storage and transport. It is found that doping nitrogen is a promis-
ing approach to enhance the capacitance. Doping nitrogen in carbon
framework can not only improve the electrolyte penetration, wet-
tability and ion-accessible of carbon materials resulting from the
hydrophilic nitrogen groups, but also provide an additional pseudo-
capacitance due to the reversible redox reaction (Sun et al., 2014).
Up to now, there has been varieties of procedures to synthesize
nitrogen-doped (N-doped) materials, such as chemical vapor depo-
sition (Jin, Yao, Kittrell, & Tour, 2011), nitrogen plasma (Wang, Shao,
Matson, Li, & Lin, 2010), thermal annealing (Li et al., 2009; Wu, Ren,
Xu, Li, & Cheng, 2011), and so on.
Traditionally, carbon materials used in supercapacitors are
mainly derived from fossil resources, and thus face severe envi-
ronmental problems and will suffer from the dissipation of fossil
resources in the near future. Biomass resources are the most abun-
dant renewable carbon sources on the earth, and are the ideal
alternatives to fossil resources for synthesis of various carbons for
supercapacitors (James et al., 2012; Ma et al., 2015; Saha et al., 2014;
Xu, Hou, Cao, Wu, & Yang, 2012; Yamagata, Soeda, Ikebe, Yamazaki,
& Ishikawa, 2013). Recently, bacterial cellulose, a typical biomass
material, has been extensively used to synthesize functional carbon
materials with 3D porous structure (Chen et al., 2013; Wu et al.,

http://dx.doi.org/10.1016/j.carbpol.2017.04.063
0144-8617/ 2017 Elsevier Ltd. All rights reserved.
108 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116
2014; Wu, Liang, Chen, Hu, & Yu, 2015). Chen, Huang, Liang, Gao,
and Yu (2014) fabricated heteroatom-doped 3D nanober network
carbon materials via a convenient pyrolysis of bacterial cellulose
with H3 PO4 , NH4 H2 PO4 , and H3 BO3 /H3 PO4 , respectively. The as-
synthesized N/P co-doped carbon nanober displayed an excellent
performance as supercapacitor electrode (204.9 F g1 at 1 A g1 ). It
is difcult, however, to obtain highly porous carbon with hierarchi-
cal pores by directly carbonizing lignocellulose due to its compact
structure (Jiang et al., 2015; Liu, Yu, Wu, Li, & Li, 2014; Weng
et al., 2011). Recently, Hao et al. (2014) fabricated porous carbon by
carbonizing freeze-drying cellulose aerogel using bagasse as raw
material. The as-synthesized porous carbon exhibited a specic
capacitance of 142.1 F g1 at 0.5 A g1 . To improve the superca-
pacitance of cellulose-based porous carbon, our group fabricated
an N-doped carbon by annealing cellulose aerogel in NH3 atmo-
sphere at high temperature, and the supercapacitance was high up
to 225 F g1 (0.5 A g1 ) (Hu et al., 2016). The N content of the porous
carbon, however, is difcult to be controlled via this method.
Herein, we demonstrate another strategy to effectively synthe-
size N-doped PC with hierarchical porous structure from cellulose
by using urea as a low-cost N source. As compared with annealing
in NH3 atmosphere, the cost of the present method is much lower.
Furthermore, the N content can be easily tuned (0.68%7.64%) by
controlling the concentration of urea aqueous solution. It was found
that the as-prepared N-doped PC-2 with an N content of 3.61% and
a high specic surface area of 471.7 m2 g1 , showed a high capac-
itance of 193 F g1 (144 F g1 for N free PC) and an outstanding
cycling stability. More importantly, the symmetric supercapaci-
tor displayed a high energy density of 17.1 W h kg1 at a power
density of 400 W kg1 . This work offers an important method to
cost-efciently synthesize N-doped PC in a scale-up manner.
2. Material and methods
2.1. Materials
Cellulose was purchased from Shanghai Aladdin Industrial Cor-
poration (China). Sodium hydroxide (NaOH), urea, tert-butanol
(tBuOH) were analytical grades and used without purication.
2.2. Preparation of cellulose aerogels
Cellulose aerogels were prepared by dissolving, gelling, adsorb-
ing urea, and free-drying process. In a typical procedure, 12 g NaOH,
7 g urea and 81 g H2 O were mixed together and precooled to 12 C.
Then 4 g cellulose was dissolved in the NaOH/urea/H2 O solution to
obtain a transparent cellulose solution. The resulting solution was
poured into a glass plate, sealed with cling lm and placed in an
oven at 50 C for 3 days to obtain cellulose gels. After being washed
with deionized water to remove residual chemical reagents, the cel-
lulose gels were immersed in urea solution (the molar ratios of urea
to H2 O were 0.01, 0.02, and 0.05, respectively) for 24 h. The cellu-
lose gels were then immersed in tBuOH for another 24 h to replace
H2 O, and nally freeze-dried in a lyophilizer (58 C, 0.22 mbar) for
24 h to obtain cellulose aerogels.
2.3. Preparation of N-doped PCs
N-doped PCs were obtained by heating urea-containing cellu-
lose aerogels in a tube furnace under owing Ar. The aerogels were
rst heated to 200 C at a heating rate of 5 C min1 and kept at
200 C for 2 h. Afterwards, the samples were heated to 800 C at a
heating rate of 3 C min1 and kept at 800 C for 2 h. The resultant
N-doped PCs were denoted as N-doped PC-1, N-doped PC-2, and
N-doped PC-5 (1, 2, and 5 represent the molar ratios of the urea
solution of 0.01 0.02, and 0.05, respectively). For comparison, cel-
lulose aerogels without urea were carbonized in the same condition
and the porous carbon was named as N-free PC.
2.4. Characterizations
The morphologies and structures of all samples were char-
acterized using transmission electron microscopy equipped with
high-resolution imaging feature (TEM, JEM-2100F) at an accel-
eration voltage of 200 kV and eld-emission scanning electron
microscope combined with EDX mapping (FE-SEM Merlin, Zeiss)
at an acceleration voltage of 5 kV. X-ray diffraction (XRD) mea-
surement was conducted by a Bruker D8 diffractometer with a
2 theta ranging from 10 to 60 using Cu-K radiation (40 kV and
40 mA, X = 0.15418 nm) as an X-ray source. The Raman spectra
were collected by a Raman spectrometer (LabRAM ARAMIS-
Horiba Jobin Yvon) operating with 532 nm excitation and the
wavenumber range used in the measurement was from 800 to
2000 cm1 . The pore structures of the samples were determined
from N2 adsorption-desorption isotherms on a physisorption ana-
lyzer (Micromeritics, ASAP 2020) at 77 K for P/P0 of 0.010.99. Prior
to adsorption experiment, all samples were degassed at 200 C
for 12 h under vacuum. Elemental analysis was measured by an
elemental analyzer (VarioEL III, Elementar). X-ray photoelectron
spectra (XPS) were recorded on Thermo Scientic ESCALAB 250Xi
spectrometer with an exciting source of Al K (1286.6 eV).
2.5. Electrochemical measurements
The electrochemical performances of all samples were inves-
tigated in 1.0 M H2 SO4 aqueous solution using a CHI660E
electrochemical workstation (CH Instruments, China). To prepare
the working electrode, the sample was skived into a slice with a
dimension of about 10 mm 10 mm 1 mm and pressed on a tita-
nium mesh.
In a three-electrode system, the above prepared electrode,
Ag/AgCl electrode and Pt wire were used as working electrode,
reference electrode and counter electrode, respectively. Cyclic
voltammetry (CV), galvanostatic charge-discharge (GCD) exper-
iments and electrochemical impedance spectroscopy (EIS) were
performed in 1.0 M H2 SO4 aqueous solution at room tempera-
ture. The CV curves were obtained at potential sweep rates of
5200 mV s1 and the GCD measurements were performed at cur-
rent densities of 0.510 A g1 within the potential window of
00.8 V. The EIS measurements were examined in the frequency
ranging from 10 mHz to 100 kHz.
The gravimetric specic capacitances of the electrodes at differ-
ent scan rates were calculated from the CV curves according to the
following equation:

I dV
C=
mV
where I is the current (A),  is the scan rate (V s1 ), V is the applied
potential window (V), and m is the mass of the working electrode
sample (g).
The specic capacitances of the electrodes at various current
densities were obtained by GCD curves using the following equa-
tion:
It
C=
mV
where I is the current loaded (A), t is the discharge time (s), V is
the applied potential window (V), and m is the mass of the working
electrode sample (g).
In a two-electrode system, two electrodes with the same mass
were used as a symmetrical supercapacitor.
 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116 109

Table 1
Structure and physicochemical parameters of all samples.

Sample SBET Smic Vt Vmic C N

(m2 g1 ) (m2 g1 ) (cm3 g1 ) (cm3 g1 ) (wt%) (wt%)

N-free PC 853 344 1.11 0.18 84.42 0

N-doped PC-1 552 392 0.45 0.21 75.83 0.68
N-doped PC-2 472 383 0.38 0.20 77.66 3.61
N-doped PC-5 450 379 0.27 0.20 79.83 7.64

The energy density and power density were calculated accord- ores with pore size of 20100 nm. The high-resolution TEM images
ing to the following equations: of N-free PC and N-doped PC-2 (Fig. 2b and d) indicate abun-
dant slits and worm-like micropores (about 1 nm) in the carbon
Ct V 2
E= walls. These micropores, together with the mesopores and macro-
2 3.6 pores, will provide a large number of channels for the diffusion and
absorption of electrolytes (Cho, Lee, & Lee, 2014). Besides, the high-
E resolution TEM images (Fig. 2b and d) indicate a few lattice fringes
P= 3600
t that are attributed to the graphitic structure of carbon, implying a
where E is the energy density (W h kg1 ), P is the power density low graphitization degree (Sun et al., 2014). The selected area elec-
(W kg1 ), Ct is the specic capacitance of the total symmetrical sys- tron diffraction (SAED) patterns (insets in Fig. 2b and d) also reveal
tem (F g1 ), V is the applied potential window (V) and t is the the amorphous or disordered structure since the observed rings are
discharge time (s). diffused (Feng et al., 2015; Liang et al., 2014).
The porous properties of all PCs are summarized in Table 1. The
N-free PC shows the highest BET specic surface area (853 m2 g1 ).
3. Results and discussion
When urea was added, the BET specic surface areas of N-doped
PCs decrease to 552, 472, and 450 m2 g1 for N-doped PC-1, N-
3.1. Physicochemical structures of hierarchical porous N-doped
doped PC-2, and N-doped PC-5, respectively. The additional C
PCs
and N elements from urea create a more compact structure and
decrease the pore volume (as revealed by SEM), and thus leading
Scheme 1 illustrates the preparation procedure, while the struc-
to a decreasing specic surface area. The nitrogen adsorption-
tures and morphologies of the represent samples are shown in Fig. 1
desorption isotherms of N-free PC and N-doped PCs (N-doped PC-2
and Fig. 2, respectively. Both N-free PC and N-doped PCs have a
as a representative sample) display a typical type-IV isotherm
typical hierarchical porous structure with abundant macropores,
pattern with a slight hysteresis loop at a high relative pressure
mesopores and micropores (Fig. 1ah). In fact, N-free PC (Fig. 1a
(0.71.0) (Fig. 3a), demonstrating the existence of mesopores and
and b) consists of short carbon rods, which is quite different from
macropores (Feng et al., 2015). A distinct increase at a low rela-
cellulose-based carbon aerogels obtained by using water as freez-
tive pressure (less than 0.1) indicates that micropores exist in the
ing media (Hao et al., 2014; Zhuo et al., 2016). When the cellulose
porous carbon (Chang et al., 2015). To take an insight into the
gel saturating with tBuOH was frozen, high freezing point of tBuOH
porous texture of the samples, the pore size distributions were
(above 25 C) allowed a quickly solidication and thus resulted
measured and shown in Fig. 3b. N-free PC and N-doped PC-2 have
in much smaller particles as compared with ice crystals resulting
wide pore distribution and exhibited sharp peaks at 3.3 nm and
from H2 O (Tong et al., 2016). These smaller particles led to much
3.8 nm, respectively, indicating abundant micropores and meso-
smaller pores. Volume shrinkage due to the losses of O, H, N, and
pores, as well as hierarchical porous structures. However, N-doped
C during carbonization at high temperature resulted in a nanorod
PC-2 has a much lower pore volume. The presence of macrop-
interconnected structure. These pores are open, forming abundant
ores and mesopores helps to reserve electrolyte ions and provides
interconnected channels. There is no signicant difference between
a shorter transport distance to guarantee the rapid diffusion of
N-free PC (Fig. 1a and b) and N-doped PC-1 (Fig. 1c and d) with a
the electrolytes. The micropores, together with mesopores, are
low urea ratio.
expected to enhance the charge storage by providing a high acces-
As compared with N-free PC and N-doped PC-1, however, the
sible surface area and more active sites (Cho et al., 2014; Zhang
short carbon rods in N-doped PC-2 are hardly to be observed and
et al., 2013).
more akes appeare in the interconnected network (Fig. 1e and
X-ray diffraction (XRD) and Raman spectroscopy were used to
f). It is supposed that urea can provide extra C and N elements to
determine the structural characterizations of samples, as shown in
offset the loss of elements during annealing, and thus resulting in
Fig. 4a and Fig. 4b, respectively. All samples have broad and low-
akes and the encapsulation of short carbon rods in the akes. A
intensity peaks centered at around 24.3 and 43.3 (Fig. 4a), which is
higher urea ratio produces more carbon akes, leading to a more
attributed to the (002) and (100) graphite plane, respectively. This
compact carbon network with less pores, as indicated by Fig. 1g and
suggests the amorphous structure and a low degree of graphitiza-
h. Therefore, urea has a remarkable impact on the porous structure
tion (Qie et al., 2012; Sun et al., 2014). Moreover, the Raman spectra
of N-doped PCs. Moreover, according to the elemental mappings
of all samples with G-band at 1578 cm1 in Fig. 4b further reveal
of N-free PC and N-doped PCs (N-doped PC-2 as a representative
the presence of graphitic carbon. The D-band centered at 1334 cm1
sample), it can be clearly seen that only C (Fig. 1j) and O (Fig. 1k)
reveals the disorded carbon or defective graphitic structure (Wang
species could be detected for N-free PC, while C (Fig. 1n), O (Fig. 1o)
et al., 2014). This kind of carbon material with partial graphitization
and N (Fig. 1p) could be observed in the elemental mapping of N-
is highly desirable for the application as an electrode material due to
doped PC-2, indicating that nitrogen has been successfully doped
its high conductivity. The graphitization degree can be determined
in the carbon network.
by the intensity ratio of G band to D band (IG /ID ), and a higher IG /ID
The typical TEM images (Fig. 2) indicate that N-free PC and N-
value indicates a higher graphitic degree and less disordered car-
doped PC-2 possess an interconnected hierachical porous structure,
bon (Dresselhaus, Dresselhaus, Saito, & Jorio, 2005; Li et al., 2013).
which is in good agreement with the results of SEM. The low-
The IG /ID values of the N-free PC, N-doped PC-1, N-doped PC-2, and
resolution TEM images (Fig. 2a and c) show that the pore walls
N-doped PC-5 are 0.36, 0.34, 0.31, 0.18, respectively, indicating that
of N-free PC and N-doped PC-2 consist of mesopores and macrop-
110 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116
Scheme 1. Illustration of the preparation procedure of cellulose-based N-doped porous carbon.
the doping N causes an increase of disordered carbon since the N
doping may break the sp2 carbon plane (Saitoh et al., 2000).
Elemental analysis and XPS were conducted to further inves-
tigate the chemical composition and surface functional groups of
N-free PC and N-doped PCs. According to the elemental analysis
results (Table 1), the N content in N-doped PCs ranges from 0.68 to
7.64 wt%, suggesting that the N content can be easily controlled by
varying the concentration of urea solution. An N content of 7.64 wt%
in N-doped PC is higher than that of cellulose based carbon fabri-
cated by activation and doping of KOH-urea (Shen, Hu, & Fan, 2014).
The XPS survey spectra of N-free PC and N-doped PCs are shown
in Figs. 4cf and S1. The low-resolution spectra (Fig. 4c) reveal the
doping N in N-doped PCs, while only carbon and oxygen species
can be detected for N-free PC. In the high-resolution C1 s spectra,
N-free PC only exhibits three peaks arising from C C (284.0 eV),
C O (285.4 eV), and C O (289.2 eV) (Fig. 4d). For N-doped PC-1 (Fig.
S1a), N-doped PC-2 (Fig. 4e), and N-doped PC-5 (Fig. S1c), however,
an additional type of carbon representing C N can be observed at
285.8 eV (Boudou, 2003; Guan et al., 2015). Similarly, the high-
resolution N1 s spectra of N-doped PC-1 (Fig. S1b), N-doped PC-2
(Fig. 4f), and N-doped PC-5 (Fig. S1d), show that four kinds of N have
been doped into the carbon network. The four peaks at 397.5, 398.1,
400.25, and 402.71 eV are attributed to pyridinic-N (N-1), graphitic-
N (N-2), pyrrolic-N (N-3), and oxidized-N (N-4) atoms (Boudou,
2003; Hao et al., 2015), respectively. Pyridinic-N and pyrrolic-N are
suggested to improve the capacitance of carbon materials because
of their pseudo-capacitive performance, while graphitic-N may
enhance the conductivity of carbon materials (Hulicova-Jurcakova,
Seredych, Lu, & Bandosz, 2009). Therefore, the hierarchical porous
carbon with partial graphitization structure and doped N atoms
will be benecial to enhance the supercapacitance of N-doped PC.
3.2. Electrochemical performances of hierarchical porous
N-doped PCs
The electrochemical performances of N-free PC and N-doped
PCs in a three-electrode system are shown in Fig. 5. The CVs of all
samples at a scan rate of 20 mV s1 show quasi-rectangular shape
(Fig. 5a), demonstrating a good capacitive behaviour. The CVs of N-
doped PCs, however, show a small hump, which can be attributed to
the combination of electrical double-layer capacitance and pseudo-
capacitance behaviours owing to the N functionalities (Guo, Su,
Kang, & Ning, 2013). The areas of N-doped PCs are larger than that
of N-free PC, indicating higher supercapacitances. Furthermore, N-
doped PC-5 exhibits a lower slope than N-doped PC-1 and N-doped
PC-2, suggesting a lower conductivity or higher resistance. Fig. 5b
also shows that the GCD of N-free PC is linear and symmetrical,
while those of N-doped PCs are not strictly symmetrical and slightly
distorted, implying the pseudo-capacitive behaviour of the active
functional groups (Sun et al., 2014). In addition, the specic capac-
itances (Cg ) calculated from GCD at 1.0 A g1 are 129, 161, 179, and
160 F g1 for N-free PC, N-doped PC-1, N-doped PC-2, and N-doped
PC-5, respectively, demonstrating that N-doped PCs have higher
supercapacitance properties than N-free PC (Fig. 5c). It is shown
that the BET specic surface areas of N-doped PCs are remarkably
lower than that of N-free PC (Table 1), and thus the improvement
in supercapacitance can be attributed to the doping N function-
alities. Impressively, N-doped PC-1 with only 0.68% N possesses
a higher supercapacitance than N-free PC, indicating that even a
little amount of doping N can remarkably enhance the superca-
pacitive performance of carbon materials. Surprisingly, the specic
capacitance (160 F g1 ) of N-doped PC-5 with a N content of high
up to 7.64% is the same to that of N-doped PC-1 (161 F g1 ) with
only 0.68% N, but lower than that of N-doped PC-2 (179 F g1 ) with
3.61% N. This may be due to that N-doped PC-5 has lower BET spe-
cic surface area (Table 1), more disordered carbon (Fig. 4b), and
less open porous structure (Fig. 1).
Fig. 5d and e shows the CVs of N-doped PC-1 and N-doped PC-2
at different scan rates ranging from 5 to 200 mV s1 . The CV curves
of N-free PC signicantly deteriorate at high scan rates (Fig. 5d),
while the CV of N-doped PC-2 remains a quasi-rectangular shape
at a scan rate of high up to 100 mV s1 (Fig. 5e), suggesting that
N-doped PC-2 has a better capacitive behaviour over a wide range
of scan rates. The doping N within the carbon network of N-doped
PC-2 is believed to contribute to the enhancement in capacitive
performance (Guo et al., 2013). Moreover, the specic capacitances
 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116 111

Fig. 1. SEM images of N-free PC (a and b), N-doped PC-1 (c and d), N-doped PC-2 (e and f), and N-doped PC-5 (g and h). SEM images of N-free PC (i) and the corresponding
elemental mapping images of C (j), O (k) and N (l). SEM images of N-doped PC-2 (m) and the corresponding elemental mapping images of C (n), O (o) and N (p).

Fig. 2. TEM images of N-free PC (a) and N-doped PC-2 (c) and high-resolution TEM images of N-free PC (b) and N-doped PC-2 (d). Insets: the corresponding selected area
electron diffraction patterns.

calculated from CV are displayed in Fig. 5f. It is clearly that the at 200 mV s1 ), while N-free PC displays a capacitance retention of
capacitance of N-doped PC-2 is higher than that of N-free PC at all only 39.7%. This suggests a better rate capability for N-doped PC-2.
scan rates. A capacitance retention of 68.1% can be acquired for N- The GCDs of N-free PC and N-doped PC-2 are shown in Fig. 5g
doped PC-2 at 200 mV s1 (341.3 F g1 at 5 mV s1 and 232.4 F g1 and Fig. 5h, respectively. The GCDs of N-free PC are linear and
112 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116

Fig. 3. N2 adsorption-desorption isotherms (a) and pore size distributions (PSD) calculated from the desorption isotherms (b) of N-free PC and N-doped PC-2.

Fig. 4. XRD patterns (a) and Raman spectra (b) of N-free PC and N-doped PCs. XPS spectra of N-free PC and N-doped PCs (c). High-resolution C1s spectra of N-free PC (d) and
N-doped PC-2 (e). High-resolution N1s spectrum of N-doped PC-2 (f).

Table 2
Comparison of electrochemical performance of various carbons.

Materialsa Capacitance (F g1 ) Condition Electrolyte Ref.

(mV s1 or A g1 )

Cellulose-derived PC 142.1 0.5 A g1 6 M KOH Hao et al. (2014)

Lignin-derived C 102.3 2 mV s1 6 M KOH Saha et al. (2014)
Potato waste-derived C 255 0.5 A g1 2 M KOH Ma et al. (2015)
Carbon nanospheres 159 10 mV s1 Yang et al. (2015)
PANI/cellulose lm 160 0.1 A g1 1 M H2 SO4 Liu et al., 2014
Filter paper-derived C 115 5 mV s1 5 M KCl Jiang et al. (2015)
N-doped CA 225 0.5 A g1 1 M H2 SO4 Hu et al. (2016)
CS-derived N-doped CA 291.8 2 mV s1 6 M KOH Hao et al. (2015)
N-doped PC-2 193 0.5 A g1 1 M H2 SO4 This work
341.3 5 mV s1
a
PC, C, CA and CS refer to porous carbon, carbon, carbon aerogel and chitosan, respectively.

symmetrical at different current densities, indicating an excellent strictly symmetrical at lower current densities, suggesting an addi-
electrochemical reversibility and coulombic efciency (Ma et al., tional pseudo-capacitance performance. As shown in Fig. 5i, the
2015; Yamagata et al., 2013). For N-doped PC-2, the GCDs are not capacitance of N-free PC is 144 F g1 at a low current density of
 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116 113

Fig. 5. CV curves (a), GCD curves (b), and specic capacitances (c) of N-free PC and N-doped PCs. CV curves of N-free PC (d) and N-doped PC-2 (e) at different scan rates. GCD
curves of N-free PC (g) and N-doped PC-2 (h) at different current densities. Specic capacitances calculated from CV curves (f) and GCD curves (i). Nyquist plots of N-free PC
and N-doped PCs (j). Insets: expanded high-frequency region of the plots and the equivalent circuit model. Cycle stability of N-free PC and N-doped PC-2 at a current density
of 1.0 A g1 (k). Inset: GCD curves of the last 10 cycles of N-doped PC-2.

0.5 A g1 and gradually decreases to 73 F g1 at a high current den-
sity of 10 A g1 , with only 50% retention. The specic capacitance
of N-doped PC-2, however, is high up to193 F g1 at 0.5 A g1 and
remains to be 141 F g1 at 10 A g1 , exhibiting a capacitance reten-
tion of 73.0%. This indicates that N-doped PC-2 has a better rate
capability (Liang, Liu, Li, Fu, & Wu, 2013). The excellent superca-
pacitance performances of N-doped PC-2 are expected to originate
from the combining effect of N functionalities, hierarchical porous
structure with large amounts of mesopores and micropores, and
good electrical conductivity resulting from the partial graphitiza-
114 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116

Fig. 6. Supercapacitance performances of the N-doped PC-2//N-doped PC-2 symmetrical supercapacitor. CV curves in different operation voltages (a). CV curves at different
scan rates (b). GCD curves at different current densities (c). Ragone plots compared with those of other carbon materials previously reported in aqueous electrolyte (d); LEDs
were lighted up by two supercapacitor devices using N-doped PC-2 as electrode material (e).

tion structure. As shown in Table 2, the capacitance of N-doped
PC-2 is not only superior to those of other cellulose-derived carbon
materials (Hao et al., 2014; Jiang et al., 2015), but also is higher than
those of other biomass-derived carbons, such as lignin (Saha et al.,
2014) and chitosan (Hao et al., 2015).
Fig. 5j displays the Nyquist plots of N-free PC and N-doped
PCs with a frequency range from 10 mHz to 100 kHz. As com-
pared with N-free PC, N-doped PC-1, and N-doped PC-5, N-doped
PC-2 has a steeper capacitive spike with an almost 90 angle
in the low-frequency region, demonstrating a better capacitive
behaviour (Feng et al., 2015). To better understand the capaci-
tance behaviour of the electrodes, an equivalent electrical circuit
model was established, as shown by the inset in Fig. 5j. The real
axis intercept corresponds to the equivalent series resistance (RS ),
which is the sum of active materials resistance, electrolyte resis-
tance, and contact resistance between active material and current
collector (Portet, Yushin, & Gogotsi, 2007). N-doped PC-2 exhibits a
RS value of 0.94  that is lower than those of N-free PC (1.03 ),
N-doped PC-1 (0.97 ), and N-doped PC-5 (1.45 ), suggesting
that N-doped PC-2 has a higher conductivity, which well agrees
with the CV curves from Fig. 5a. In addition, the radius of the
semicircle impedance of electrode material commonly represents
charge-transfer resistance (Rct ) between electrode material and the
electrolyte (Guo, Song, & Chen, 2009). As compared with N-free
PC, N-doped PC-2 displays a smaller semicircle impedance at high
frequency region, demonstrating a lower Rct on the electrode sur-
face. Zw is the Warburg resistance reecting the ion diffusion in
the electrolyte. C and Q represent the capacitor layer developing
during the charge/discharge process (Liang et al., 2014; Sun et al.,
2014). The above EIS results further prove that N-doped PC-2 has
a better supercapacitance. Moreover, excellent cycling stability is
another crucial characteristic for high-performance supercapaci-
tor. As shown in Fig. 5k, the capacitance retentions of N-free PC
and N-doped PC-2 are high up to 106% and 107% respectively, after
5000 cycles, which indicates an outstanding stability. The slightly
increasing capacitance after 5000 cycles may be ascribed to that
more micropores could be utilized to store ions during the long-
cycle duration (Wu et al., 2012; Yuan et al., 2013).
In order to further explore the practical application of N-doped
PC for supercapacitor, a two-electrode behaviour from symmetric
supercapacitor of N-doped PC-2 was investigated in 1.0 M H2 SO4 ,
as shown in Fig. 6. The symmetric supercapacitor can be cycled
reversibly within the voltage window of 01.6 V (Fig. 6a), and
the CVs at various scan rates display a rectangular-like shape
even at a high scan rate of 100 mV s1 (Fig. 6b); while the GCDs
(Fig. 6c) at different current densities (from 0.5 to 5 A g1 ) exhibit
relatively symmetric triangle shapes, suggesting a good electro-
chemical capacitive behaviour (Long, Chen, Jiang, Zhi, & Fan, 2015;
Wang et al., 2014). The energy densities and power densities of the
symmetric supercapacitor calculated from GCDs are displayed in
Fig. 6d. The symmetric supercapacitor exhibits a maximum energy
density of 17.1 W h kg1 at a power density of 400 W kg1 , which
is not only comparable to those of B/N co-doped carbon (Ling
et al., 2016), N-doped carbon (Zhang et al., 2016), and function-
alized graphene (Tian et al., 2015), but also superior to those of
other biomass-derived carbons (Farma et al., 2013; Liang et al.,
2014; Qu, Xu, Lu, Zhang, & Li, 2015; Yang, Jang, & Jeong, 2014),
hierarchical porous carbon (Wang et al., 2014), 3D micro-porous
carbon (Puthusseri, Aravindan, Madhavi, & Ogale, 2014), and S-
doped micro/mesoporous carbon (Seredych and Bandosz, 2013).
Finally, we assembled two supercapacitor devices using N-doped
PC-2 as electrode material to light up four light-emitting-diodes
 Z. Chen et al. / Carbohydrate Polymers 170 (2017) 107116
(LED) for more than 2 min (Fig. 6e), suggesting a practical applica-
tion of N-doped PC-2 for energy storage system.
Thus, the excellent electrochemical performance of N-doped
PC-2 can be attributed to: 1) the hierarchical porous structure
with a high specic surface area ensures the fast transfer and ef-
cient diffusion of electrolytes; 2) the partial graphitization structure
guarantees a good conductivity; 3) N atoms located in the carbon
network favor the wettability of carbon materials to electrolyte and
ion/electron transport and storage.
4. Conclusions
We demonstrated a simple and economical strategy for fabri-
cating hierarchical porous N-doped carbons with easily tunable
N content. N doping by using urea as an N source could signif-
icantly improve the supercapacitance behaviour of hierarchical
porous carbon. N-doped PC-2 with an N content of 3.61% exhibited
a high specic capacitance of 193 F g1 and a long-term durabil-
ity of 107% after 5000 cycles. Moreover, in a two-electrode system,
the symmetric supercapacitor based on N-doped PC-2 electrode,
reveals a high energy density of 17.1 W h kg1 at a power density
of 400 W kg1 . These features, together with superior advantages
of the raw material (cellulose) such as renewability, low cost, and
environment benet, make this N-doped PC a promising porous
carbon for energy storage, adsorption, catalysis, and gas storage.
Acknowledgements
This work was supported by National Natural Science
Foundation of China (21506068), Pearl River S&T Nova Pro-
gram of Guangzhou, Guangdong natural Science Foundation
(2014A030310319 and 2016A030313487), Guangdong Natural Sci-
ence Funds for Distinguished Young Scholar (2015A010105005),
Science and Technology Program of Guangzhou (201504010033),
and Fundamental Research Funds for the Central Universities.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.carbpol.2017.04.
063.
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