Electrochimica Acta 90 (2013) 492–497

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Superhigh capacity and rate capability of high-level nitrogen-doped graphene

sheets as anode materials for lithium-ion batteries
Dandan Cai a , Suqing Wang a , Peichao Lian b , Xuefeng Zhu c , Dongdong Li a ,
Weishen Yang c , Haihui Wang a,∗
a
School of Chemistry and Chemical Engineering, South China University of Technology, Wushan Road, Guangzhou, China
b
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming, China
c
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

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

Article history: A new facile approach is proposed to synthesize nitrogen-doped graphene sheets with the nitrogen-
Received 27 September 2012 doping level as high as 7.04 at.% by thermal annealing pristine graphene sheets and low-cost industrial
Received in revised form material melamine. The high-level nitrogen-doped graphene sheets exhibit a superhigh initial reversible
23 November 2012
capacity of 1123 mAh g−1 at a current density of 50 mA g−1 . More significantly, even at an extremely high
Accepted 26 November 2012
current density of 20 A g−1 , highly stable capacity of about 241 mAh g−1 could still be obtained. Such an
Available online 16 December 2012
electrochemical performance is superior to those previously reported nitrogen-doped graphene sheets.
The excellent electrochemical performance can be attributed to the two-dimensional structure, disor-
Keywords:
Nitrogen-doped
dered surface morphology, high nitrogen-doping level, and the existence of pyridinic nitrogen atoms. The
Graphene sheets results indicate that the high-level nitrogen-doped graphene sheets could be a promising anode material
Anode material for high-performance lithium-ion batteries.
Lithium-ion batteries © 2012 Elsevier Ltd. All rights reserved.

1. Introduction batteries [21–24]. Recently, nitrogen-doped graphene has been

Lithium-ion batteries play an important role in portable elec-
tronic devices because of their high energy density, long cycling
lifetime and excellent safety. In recent years, they have also been
proposed for being applied in hybrid electric vehicles and electric
vehicles, which promoted the great research interests in developing
lithium-ion batteries with high reversible capacity, excellent rate
performance and cycling stability [1,2]. Graphite, the commercial
anode material, also encounters some disadvantages such as low
theoretical specific capacity (372 mAh g−1 ) and poor rate perfor-
mance [3]. Thus, it is imperative to develop new high-performance
electrode materials for lithium-ion batteries.
Graphene has been considered to be a promising anode mate-
rial for lithium-ion batteries and exhibits a large reversible specific
capacity due to its large surface area, superior electronic con-
ductivity and high chemical stability [4–10]. In addition, the
electronic and chemical properties of graphene can be modified
by chemical doping heteroatoms, such as boron atoms and nitro-
gen atoms [11–15]. Particularly, nitrogen-doped graphene has
been extensively applied in various fields, such as electrocatalysis
[16,17], supercapacitor [18,19], Li-air fuel cell [20], and lithium-ion
∗ Corresponding author. Tel.: +86 20 87110131; fax: +86 20 87110131.
E-mail address: hhwang@scut.edu.cn (H. Wang).
widely investigated and delivers better electrochemical perfor-
mance than the pristine graphene [21–24]. The high nitrogen-
doping level could help improve the rate capability and reversible
capacity of the nitrogen-doped graphene sheets because of the
more disorder degree induced [12,23,25]. The pyridinic nitrogen
atoms could also be beneficial to increase the reversible capacity of
the nitrogen-doped graphene electrode, which could be attributed
to the stronger electronegativity of nitrogen than that of carbon
[20,25–27]. However, the synthetic methods of nitrogen-doped
graphene are mainly limited to chemical vapor deposition (CVD)
[20], thermal annealing of graphene oxide with NH3 [28], nitro-
gen plasma treatment of graphene [29], solvothermal synthesis
[30], and the arc-discharge method [31]. The CVD method can-
not meet the demand of large scale production of nitrogen-doped
graphene [21]. Besides, nitrogen-doping level of the nitrogen-
doped graphene prepared by NH3 gas thermal treatment method
is low (2–4%), and NH3 is a corrosive gas. Additionally, the last
three methods are complicated and high cost. Therefore, it is still
a challenge to prepare nitrogen-doped graphene sheets with high
nitrogen doping level by a facile method.
Herein, we propose a simple and facile approach to synthesize
high-level nitrogen-doped graphene sheets by thermal anneal-
ing pristine graphene sheets and low-cost industrial material
melamine. The electrochemical performance of the obtained
material was investigated, and compared with those previously

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.11.105
 D. Cai et al. / Electrochimica Acta 90 (2013) 492–497
Fig. 1. The TEM images of (a) the graphene sheets and (b) the nitrogen-doped graphene sheets.
reported nitrogen-doped graphene sheets. The as-prepared
nitrogen-doped graphene sheets as anode materials for lithium-
ion batteries show a superhigh specific capacity and excellent rate
performance.
2. Experimental
2.1. Materials preparation
Nitrogen-doped graphene sheets were prepared via a simple
thermal annealing approach involving pristine graphene sheets and
low-cost industrial material melamine. First, the pristine graphene
sheets were prepared by rapid thermal expansion method accord-
ing to our previous report [10]. Then, the pristine graphene sheets
and melamine (Tianjin Kermel Chemical Reagent Co., Ltd., China)
were mixed together with a weight ratio of 1:6 by grinding for
2 h. The mixture in a combustion boat was then placed in the
center of a quartz tube in argon gas atmosphere and heated to
700 ◦ C at a heating rate of 5 ◦ C/min. After the temperature was
maintained for 1 h, the furnace was cooled to room temperature
slowly. The final product was taken out of the combustion boat.
For comparison, the graphene sheets were prepared under the
same thermal treatment condition without adding melamine. In
addition, the bare melamine powder was also annealed in the
combustion boat under the same condition without adding the pris-
tine graphene sheets. After the reaction was finished, carbonized
melamine was found and collected in the inner wall of mouth of the
quartz tube.
2.2. Characterization of materials
The structure and morphology were characterized by transmis-
sion electron microscopy (TEM) (FEI, Tecnai G2 F30 S-Twin). Raman
spectra were measured using a Horiba Jobin Yvon LabRam Aramis
Raman spectrometer with a laser of 632.8 nm. X-ray photoelec-
tron spectroscopy (XPS) analysis was carried out using an ESCALAB
250 spectrometer (Thermo Fisher Scientific) with the mono Al
K␣ radiation (1486.6 eV) under a pressure of 2 × 10−9 Torr. Ele-
mental analysis was carried out with pure oxygen combustion
method (vario EL III elementar, Germany). The nitrogen content
in the nitrogen-doped graphene sheets was obtained by burning
the sample to form oxynitride, which can be detected by a thermal
conductivity detector (TCD).
493
2.3. Electrochemical measurements
The electrochemical performances of the nitrogen-doped
graphene sheets and the graphene sheets were investigated using
coin cells (CR2025). The slurry contained the active materials (the
nitrogen-doped graphene sheets or the graphene sheets) (75 wt.%),
Super P (15 wt.%), and poly(vinylidene fluoride) (PVDF, Kureha,
Japan) binder (10 wt.%) in an N-methyle-2-pyrrolidone (NMP, Tian-
jin Kermel Chemical Reagent Co., Ltd., China) solvent was pasted on
a copper foil. Highly pure lithium foil was used as the counter elec-
trode. Meanwhile, the celgard 2325 membrane was used as the
separator. The electrolyte was composed of 1 mol L−1 LiPF6 dis-
solved in a mixture of ethylene carbonate (EC) and diethylcarbonate
(DEC) (1:1 by volume) (Beijing Institute of Chemical Reagents,
China). The coin cells were assembled in an argon-filled glove box
(Mikrouna, super 1220) where the oxygen and moisture contents
were less than 1 ppm. The cells were galvanostatically discharged
and charged using a Battery Testing System (Neware Electronic Co.,
China) between 0.01 and 3.0 V.
3. Results and discussion
3.1. Microstructural characterization
Fig. 1 shows representative TEM images of the graphene sheets
and the nitrogen-doped graphene sheets. It can be clearly observed
that the nitrogen-doped graphene sheets still maintain the two-
dimensional ultrathin flexible structure of the graphene sheets
[4,5]. However, nitrogen-doped graphene sheets have more corru-
gations and scrolling than the graphene sheets, which is attributed
to the defective structures formed by chemical doping nitrogen
atoms [16,23]. The disordered structures in the nitrogen-doped
graphene sheets could increase lithium storage sites, which is well
consistent with the results of electrochemical performance.
Raman spectra of the nitrogen-doped graphene sheets and the
graphene sheets are shown in Fig. 2. The Raman spectrum of the
nitrogen-doped graphene sheets displays two dominant peaks at
about 1326 and 1590 cm−1 corresponding to the D band and G
band, respectively. Moreover, the G band of the nitrogen-doped
graphene sheets is down-shifted to 1590 cm−1 compared with the
graphene sheets (1591 cm−1 ). The downshift of the G band can be
attributed to electron-donating capability of nitrogen heteroatoms
494 D. Cai et al. / Electrochimica Acta 90 (2013) 492–497

a Survey C1s
N-doped graphene sheets
N1s O1s
D

Intensity / a.u.
1326 1590 Carbonized melamine
Intensity / a.u.

1324
a
Graphene sheets
1591

b
Pristine graphene sheets

1000 1200 1400 1600 1800 0 200 400 600 800 1000
Raman Shift / cm-1 Binding Energy / eV

Fig. 2. Raman spectra of (a) the nitrogen-doped graphene sheets and (b) the
graphene sheets. b C 1s 284.8
N-doped graphene sheets

[16,17,32,33]. As is known, the G band with E2g symmetry is related

to phonon vibrations in sp2 carbon materials, while the D band with

Intensity / a.u.
A1g symmetry is ascribed to disordered carbon, edge defects, and
other defects [32,33]. Generally, the intensity ratio of D band to G 285.3
band (ID /IG ) is used to estimate the disorder degree of graphene. As
shown in Fig. 2, the nitrogen-doped graphene sheets show appar-
ently higher ID /IG (1.29) than the graphene sheets (0.86), suggesting
that the nitrogen-doping process generates extrinsic defects on the 286.6
graphene surface [34].
Table 1 shows carbon, oxygen and nitrogen content of the sam-
ples obtained by XPS. It can be seen from Table 1 that the oxygen
content of the pristine graphene sheets is 9.47 at.%, which is much
higher than that of the nitrogen-doped graphene sheets (4.21 at.%).
280 282 284 286 288 290 292
We also tested the oxygen content of graphene sheets by XPS.
After high temperature thermal treatment, the oxygen content Binding Energy / eV
of graphene sheets is decreased to 5.68 at.%, indicating that the
pristine graphene sheets were partly reduced under a high temper-
ature. The phenomenon is consistent with the previously reported c N 1s N-doped graphene sheets
[8,22]. The difference of the oxygen contents of the three sam-
398.4
ples shows nitrogen-doping and reduction of residual oxygen of
the pristine graphene sheets was achieved simultaneously in the
Intensity / a.u.

thermal annealing process [16,19,35,36].

The binding energies in the XPS analysis were corrected with
reference to the C 1s peak (284.8 eV). In Fig. 3a, the appearance 400.9
of N 1s peak in the spectrum indicates that nitrogen was success- 399.6
fully doped into graphene sheets for the nitrogen-doped graphene
sheets. Moreover, an atomic percentage of doped nitrogen is about
7.04 at.% based on XPS, which is higher than that of the previ-
ously reported for lithium-ion batteries [22–24]. For example, Sun’s
group [22] synthesized nitrogen-doped graphene nanosheets by
annealing graphene sheets in the presence of ammonia gas (NH3 )
and the nanosheets contain 2.8 at.% nitrogen. Moreover, Cheng and
his coworkers [23] also made the nitrogen-doped graphene with 394 396 398 400 402 404 406
nitrogen-doping level of 3.06% by thermal treatment of the pris- Binding Energy / eV
tine graphene in mixed gas atmosphere of NH3 and argon, and
found that the rate capability of the doped graphene at high current Fig. 3. (a) The XPS spectra of the nitrogen-doped graphene sheets and carbonized
melamine; (b) C 1s XPS spectra and (c) N 1s XPS spectra of the nitrogen-doped
graphene sheets.
Table 1
Carbon, oxygen and nitrogen content (at.%) of the samples obtained by XPS.

Samples C O N rates can be further improved with increasing doping concentra-

Pristine graphene sheets 90.53 9.47 – tion in graphene. Cui’s group [24] also synthesized nitrogen-doped
Nitrogen-doped graphene sheets 88.75 4.21 7.04 graphene nanosheets with a doping level of ca. 2% nitrogen. It
Graphene sheets 94.32 5.68 – should be noted that the melamine plays an important role in the
Carbonized melamine 41.06 4.39 54.55
forming process of high-level nitrogen-doped graphene sheets. It
 D. Cai et al. / Electrochimica Acta 90 (2013) 492–497 495

can be seen from Fig. 3a and Table 1 that the nitrogen content of a st
the carbonized melamine is as high as 54.55 at.%. The high nitrogen 3.0 discharge 1
st
content could provide enough nitrogen atoms in the forming pro- charge 1

Potential vs. (Li/Li+) / V

cess of nitrogen-doped graphene sheets. According to the above 2.5 nd
discharge 2
results, the possible nitrogen doping mechanism was discussed. charge 2
nd

The oxygen-containing groups of the pristine graphene sheets were 2.0 rd

discharge 3
partly removed at high temperature and as a result formed active rd
charge 3
sites for nitrogen doping into graphene framework. Meanwhile, 1.5
th
discharge 4
nitrogen atoms or other nitrogen species formed by decomposition
th
of melamine can attack these active sites and form nitrogen-doped 1.0 charge 4
th
graphene sheets [16,36]. discharge 5
As shown in Fig. 3b, the main peak at 284.8 eV is related to the 0.5 th
charge 5
graphite-like sp2 C, which indicates that most of the C atoms in the
nitrogen-doped graphene sheets are arranged in a conjugated hon- 0.0
eycomb lattice. The two weak peaks located at 285.3 and 286.6 eV
0 500 1000 1500 2000 2500 3000
represent N C (sp2 ) and N C (sp3 ) bonds, respectively [23]. Simi-
larly, the N 1s peak can be divided into three components centered Specific Capacity / mAh g-1
at 398.4, 399.6, and 400.9 eV, representing pyridine, pyrrolic, and
graphitic nitrogen atoms in the nitrogen-doped graphene sheets, b st
3.0 discharge 1
respectively [16,17,21–24]. From Fig. 3c, the pyridine nitrogen st
atom has been found to be the main form of nitrogen in the as- charge 1
nd

Potential vs. (Li/Li+) / V

2.5
prepared nitrogen-doped graphene sheets [16,37]. discharge 2
nd
charge 2
2.0
3.2. Electrochemical properties of the nitrogen-doped graphene discharge 3
rd

sheets and the graphene sheets charge 3

rd
1.5
th
discharge 4
The first five discharge/charge profiles of the nitrogen-doped th
graphene sheets and the graphene sheets at the current density 1.0 charge 4
th
of 50 mA g−1 are shown in Fig. 4a and b, respectively. Both the discharge 5
0.5 th
nitrogen-doped graphene sheets and the graphene sheets have charge 5

the similar charge/discharge curves [22–24]. The presence of the

plateau at about 0.9 V in the first cycle could be attributed to the for- 0.0
mation of solid electrolyte interface (SEI) film on the surface of the 0 400 800 1200 1600 2000
graphene sheets [10,23,38,39]. The first reversible specific capac-
Specific Capacity / mAh g-1
ity of nitrogen-doped graphene sheets is as high as 1123 mAh g−1 ,
which is much higher than that of the graphene sheets (around Fig. 4. First five discharge/charge profiles of (a) the nitrogen-doped graphene sheets
848 mAh g−1 ). Moreover, the high-level nitrogen-doped graphene and (b) the graphene sheets at the current density of 50 mA g−1 .
sheets possess higher reversible specific capacity than those previ-
ously reported nitrogen-doped graphene sheets (684 mAh g−1 after at an extremely high current density of 20 A g−1 , high stable capac-
501 cycles [22], 1040 mAh g−1 at a low rate of 50 mA g−1 [23], and ity of about 241 mAh g−1 could still be obtained in nitrogen-doped
900 mAh g−1 at a low current density of 42 mA g−1 [24]). The rea- graphene sheets, which is higher than the value of the graphene
sons for the superhigh reversible capacity are likely to be the large sheets electrode (about 112 mAh g−1 ) and the previously reported
number of surface defects, presence of the pyridicnic N, and high- nitrogen-doped graphene sheets (199 mA g−1 at 25 A g−1 ) [23].
level nitrogen doping [12,22,24–26,40]. Notably, the charge curves
of the nitrogen-doped graphene sheets were almost consistent in
the subsequent cycles, which could be attributed to the more stable 2600 N-doped graphene sheets charge
SEI film forming during the first discharge process in the nitrogen- N-doped graphene sheets discharge
2400
doped graphene sheets.
Specific Capacity / mAh g -1

Graphene sheets charge

Fig. 5 presents the reversible charge/discharge capacity versus 2200 Graphene sheets discharge
cycle number of the nitrogen-doped graphene sheets and the
graphene sheets at the current density of 50 mA g−1 between 2000
0.01 and 3.0 V. The nitrogen-doped graphene sheets exhibit better
cycling stability and higher specific capacities than the graphene 1200
sheets. The reversible capacities of the nitrogen-doped graphene
sheets are about 1123 mAh g−1 in the first cycle and 1136 mAh g−1 900
after 50 cycles. For the graphene sheets, the reversible capacities
only are 848 mAh g−1 in the first cycle and 741 mAh g−1 after 50 600
cycles. The increase in the reversible capacities of the nitrogen-
doped graphene sheets over the graphene sheets could be ascribed 300
to the topological defects on the graphene sheets [21,23].
Fig. 6 shows the rate capabilities and cycle performance of 0
nitrogen-doped graphene sheets and the graphene sheets elec- 0 10 20 30 40 50
trodes at various current densities from 0.5 to 20 A g−1 . At a current Cycle Number
density of 0.5 A g−1 , the nitrogen-doped graphene sheets can be
Fig. 5. Reversible charge/discharge capacity versus cycle number of the nitrogen-
reversibly charged to 608 mAh g−1 , while the corresponding value doped graphene sheets and the graphene sheets at the current density of 50 mA g−1
of the graphene sheets is only 445 mAh g−1 . More significantly, even between 0.01 and 3.0 V.
496
1700
1600 N-doped graphene sheets charge
N-doped graphene sheets discharge
Specific Capacity / mAh g -1
1500
Graphene sheets charge
1400
Graphene sheets discharge
1300
700 -1
0.5 A g
600
-1
1Ag
500
400 -1
5Ag -1
10 A g
300 15 A g 20 A g-1
200
100
0 References
0 10 20 30 40
Cycle Number
Fig. 6. Rate capabilities and cycle performance of nitrogen-doped graphene sheets
and the graphene sheets electrodes at various current densities, from 0.5 to 20 A g−1 .
Fig. 7. A schematic model of lithium-ion storage in defects.
Additionally, when the current density is tuned back to 0.5 A g−1
after cycling at different rates, the specific capacities could increase
back to 674 mAh g−1 , which is higher than the value of the first
ten cycles at a current density of 0.5 A g−1 . The increased capacity
with cycling could be attributed to the activation process of the
high-level nitrogen doping anode materials [12].
The more excellent rate capability of nitrogen-doped graphene
sheets over the graphene sheets can be attributed to the following
reasons. Firstly, nitrogen-doping could induce a lot of topologi-
cal defects on the graphene sheets surface and increase disorder
degree of graphene sheets, which further increase lithium stor-
age sites of graphene sheets (as shown in Fig. 7) [24,41]. Secondly,
the pyridinic nitrogen atoms could enhance the reversible specific
capacities of the nitrogen-doped graphene sheets electrode com-
pared with the graphene sheets electrode [20,26,42]. Thirdly, high
nitrogen-doping level in nitrogen-doped graphene sheets could be
beneficial to the high reversible capacity [12,25,42].
4. Conclusions
High-level nitrogen-doped graphene sheets have been suc-
cessfully prepared by a new facile approach using the low-cost
industrial material melamine as the nitrogen source. The atomic
percentage of nitrogen in the nitrogen-doped graphene sheets
is as high as 7.04 at.%. The high-level nitrogen-doped graphene
sheets present a high reversible specific capacity of 1123 mAh g−1
at the current density of 50 mA g−1 and excellent rate capacity of
about 241 mAh g−1 , even at an extremely high current density of
20 A g−1 . Compared with existing nitrogen-doped graphene, the as-
prepared high-level nitrogen-doped graphene sheets show more
excellent electrochemical performance. The results demonstrate
D. Cai et al. / Electrochimica Acta 90 (2013) 492–497
that the high-level nitrogen-doped graphene sheets are promising
candidates as anode materials for high-performance lithium-ion
batteries.
-1
0.5 A g Acknowledgements
This work was financially supported by the National Natural Sci-
ence Foundation of China (no. 20936001), the Cooperation Project
in Industry, Education and Research of Guangdong Province and
Ministry of Education of China (no. 2010B090400518) and the
-1
Fundamental Research Funds for the Central Universities, SCUT
(2009220038).
50 60 70
[1] H. Li, Z. Wang, L. Chen, X. Huang, Research on advanced materials for Li-ion
Batteries, Advanced Materials 21 (2009) 4593.
[2] W.J. Zhang, A review of the electrochemical performance of alloy anodes for
lithium-ion batteries, Journal of Power Sources 196 (2011) 13.
[3] J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium
batteries, Nature 414 (2001) 359.
[4] A.K. Geim, K.S. Novoselov, The rise of graphene, Nature Materials 6 (2007) 183.
[5] A.K. Geim, Graphene: status and prospects, Science 324 (2009) 1530.
[6] E. Yoo, J. Kim, E. Hosono, H. Zhou, T. Kudo, I. Honma, Large reversible Li storage
of graphene nanosheet families for use in rechargeable lithium ion batteries,
Nano Letters 8 (2008) 2277.
[7] P. Guo, H. Song, X. Chen, Electrochemical performance of graphene nanosheets
as anode material for lithium-ion batteries, Electrochemistry Communications
11 (2009) 1320.
[8] D. Pan, S. Wang, B. Zhao, M. Wu, H. Zhang, Y. Wang, Z. Jiao, Li storage properties
of disordered graphene nanosheets, Chemistry of Materials 21 (2009) 3136.
[9] G. Wang, X. Shen, J. Yao, J. Park, Graphene nanosheets for enhanced lithium
storage in lithium ion batteries, Carbon 47 (2009) 2049.
[10] P. Lian, X. Zhu, S. Liang, Z. Li, W. Yang, H. Wang, Large reversible capacity of
high quality graphene sheets as an anode material for lithium-ion batteries,
Electrochimica Acta 55 (2010) 3909.
[11] S.S. Yu, W.T. Zheng, Effect of N/B doping on the electronic and field emission
properties for carbon nanotube, carbon nanocone, and graphene nanoribbon,
Nanoscale 2 (2010) 1069.
[12] L. Qie, W.M. Chen, Z.H. Wang, Q.G. Shao, X. Li, L.X. Yuan, X.L. Hu, W.X. Zhang, Y.H.
Huang, Nitrogen-doped porous carbon nanofiber webs as anodes for lithium
ion batteries with a superhigh capacity and rate capability, Advanced Materials
24 (2012) 2047.
[13] Y. Xue, B. Wu, L. Jiang, Y. Guo, L. Huang, J. Chen, J. Tan, D. Geng, B. Luo, W.
Hu, G. Yu, Y. Liu, Low temperature growth of highly nitrogen-doped single
crystal graphene arrays by chemical vapor deposition, Journal of the American
Chemical Society 134 (2012) 11060.
[14] H. Wang, T. Maiyalagan, X. Wang, Review on recent progress in nitrogen-doped
graphene: synthesis, characterization, and its potential applications, ACS Catal-
ysis 2 (2012) 781.
[15] D. Golberg, Y. Bando, Y. Huang, T. Terao, M. Mitome, C. Tang, C. Zhi, Boron nitride
nanotubes and nanosheets, ACS Nano 4 (2010) 2979.
[16] Z.H. Sheng, L. Shao, J.J. Chen, W.J. Bao, F.B. Wang, X.H. Xia, Catalyst-free syn-
thesis of nitrogen-doped graphene via thermal annealing graphene oxide with
melamine and its excellent electrocatalysis, ACS Nano 5 (2011) 4350.
[17] Z. Lin, G. Waller, Y. Liu, M. Liu, C.P. Wong, Facile synthesis of nitrogen-doped
graphene via pyrolysis of graphene oxide and urea, and its electrocatalytic
activity toward the oxygen-reduction reaction, Advanced Energy Materials 2
(2012) 884.
[18] B. Jiang, C. Tian, L. Wang, L. Sun, C. Chen, X. Nong, Y. Qiao, H. Fu, Highly con-
centrated, stable nitrogen-doped graphene for supercapacitors: simultaneous
doping and reduction, Applied Surface Science 258 (2012) 3438.
[19] L. Sun, L. Wang, C. Tian, T. Tan, Y. Xie, K. Shi, M. Li, H. Fu, Nitrogen-doped
graphene with high nitrogen level via a one-step hydrothermal reaction of
graphene oxide with urea for superior capacitive energy storage, RSC Advances
2 (2012) 4498.
[20] E. Yoo, J. Nakamura, H. Zhou, N-doped graphene nanosheets for Li -air fuel cells
under acidic conditions, Energy and Environmental Science 5 (2012) 6928.
[21] A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M. Ajayan,
Synthesis of nitrogen-doped graphene films for lithium battery application,
ACS Nano 4 (2010) 6337.
[22] X. Li, D. Geng, Y. Zhang, X. Meng, R. Li, X. Sun, Superior cycle stability of
nitrogen-doped graphene nanosheets as anodes for lithium ion batteries, Elec-
trochemistry Communications 13 (2011) 822.
[23] Z.S. Wu, W. Ren, L. Xu, F. Li, H.M. Cheng, Doped graphene sheets as anode
materials with superhigh rate and large capacity for lithium ion batteries, ACS
Nano 5 (2011) 5463.
[24] H. Wang, C. Zhang, Z. Liu, L. Wang, P. Han, H. Xu, K. Zhang, S. Dong, J. Yao,
G. Cui, Nitrogen-doped graphene nanosheets with excellent lithium storage
properties, Journal of Materials Chemistry 21 (2011) 5430.
 D. Cai et al. / Electrochimica Acta 90 (2013) 492–497
[25] Y. Wu, S. Fang, Y. Jiang, Effects of nitrogen on the carbon anode of a lithium
secondary battery, Solid State Ionics 120 (1999) 117.
[26] C. Ma, X. Shao, D. Cao, Nitrogen-doped graphene nanosheets as anode materials
for lithium ion batteries: a first-principles study, Journal of Materials Chemistry
22 (2012) 8911.
[27] Y.F. Li, Z. Zhou, L.B. Wang, CNx nanotubes with pyridinelike structures: p-
type semiconductors and Li storage materials, Journal of Chemical Physics 129
(2008) 104703.
[28] X. Wang, X. Li, L. Zhang, Y. Yoon, P.K. Weber, H. Wang, J. Guo, H. Dai, N-doping
of graphene through electrothermal reactions with ammonia, Science 8 (2009)
324.
[29] H.M. Jeong, J.W. Lee, W.H. Shin, Y.J. Choi, H.J. Shin, J.K. Kang, J.W. Choi, Nitrogen-
doped graphene for high-performance ultracapacitors and the importance of
nitrogen-doped sites at basal planes, Nano Letters 11 (2011) 2472.
[30] D. Deng, X. Pan, L. Yu, Y. Cui, Y. Jiang, J. Qi, W.X. Li, Q. Fu, X. Ma, Q. Xue, G. Sun,
X. Bao, Towards N-doped graphene via solvothermal synthesis, Chemistry of
Materials 23 (2011) 1188.
[31] L.S. Panchakarla, K.S. Subrahmanyam, S.K. Saha, A. Govindaraj, H.R. Krish-
namurthy, U.V. Waghmare, C.N.R. Rao, Synthesis, structure, and properties
of boron- and nitrogen-doped graphene, Advanced Materials 21 (2009)
4726.
[32] K.N. Kudin, B. Ozbas, H.C. Schniepp, R.K. Prud’homme, I.A. Aksay, R. Car, Raman
spectra of graphite oxide and functionalized graphene sheets, Nano Letters 8
(2008) 36.
[33] A.C. Ferrari, Raman spectroscopy of graphene and graphite: disorder, electron-
phonon coupling, doping and nonadiabatic effects, Solid State Communications
143 (2007) 47.
497
[34] W.H. Shin, H.M. Jeong, B.G. Kim, J.K. Kang, J.W. Choi, Nitrogen-doped multi-
wall carbon nanotubes for Lithium storage with extremely high capacity, Nano
Letters 12 (2012) 2283.
[35] C. Xiong, Z. Wei, B. Hu, S. Chen, L. Li, L. Guo, W. Ding, X. Liu, W. Ji, X. Wang,
Nitrogen-doped carbon nanotubes as catalysts for oxygen reduction reaction,
Journal of Power Sources 215 (2012) 216.
[36] Z. Lin, M.K. Song, Y. Ding, Y. Liu, M. Liu, C. Wong, Facile preparation of nitrogen-
doped graphene as a metal-free catalyst for oxygen reduction reaction, Physical
Chemistry Chemical Physics 14 (2012) 3381.
[37] T. Sharifi, F. Nitza, H.R. Barzegar, C.W. Tai, M. Mazurkiewicz, A. Malolep-
szy, L. Stobinski, T. Wågberg, Nitrogen doped multi walled carbon nanotubes
produced by CVD-correlating XPS and Raman spectroscopy for the study of
nitrogen inclusion, Carbon 50 (2012) 3535.
[38] D. Aurbach, Y. Ein-Eli, The study of Li-graphite intercalation processes in several
electrolyte systems using in situ X-ray diffraction, Journal of The Electrochem-
ical Society 142 (1995) 1746.
[39] W. Xing, J.R. Dahn, Study of irreversible capacities for Li insertion in hard and
graphitic carbons, Journal of The Electrochemical Society 144 (1997) 1195.
[40] H.F. Xiang, Z.D. Li, K. Xie, J.Z. Jiang, J.J. Chen, P.C. Lian, J.S. Wu, Y. Yu, H.H. Wang,
Graphene sheets as anode materials for Li-ion batteries: preparation, structure,
electrochemical properties and mechanism for lithium storage, RSC Advances
2 (2012) 6792.
[41] N.A. Kaskhedikar, J. Maier, Lithium storage in carbon nanostructures, Advanced
Materials 21 (2009) 2664.
[42] D.H. Wu, Y.F. Li, Z. Zhou, First-principles studies on doped graphene as anode
materials in lithium-ion batteries, Theoretical Chemistry Accounts 130 (2011)
209.