Vous êtes sur la page 1sur 9

Electrochimica Acta 171 (2015) 156164

Contents lists available at ScienceDirect

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

N-doped graphene/graphite composite as a conductive agent-free


anode material for lithium ion batteries with greatly enhanced
electrochemical performance
Wu Guanghui a , Li Ruiyi a , Li Zaijun a,b, * , Liu Junkang a , Gu Zhiguo a , Wang Guangli a
a
b

School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Wuxi 214122, China

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 15 January 2015
Received in revised form 22 April 2015
Accepted 4 May 2015
Available online 5 May 2015

Present graphite anode cannot meet the increasing requirement of electronic devices and electric
vehicles due to its low specic capacity, poor cycle stability and low rate capability. The study reported a
promising N-doped graphene/graphite composite as a conductive agent-free anode material for lithium
ion batteries. Herein, graphite oxide and urea were dispersed in ultrapure water and partly reduced by
ascorbic acid. Followed by mixing with graphite and hydrothermal treatment to produce graphene oxide/
graphite hydrogel. The hydrogel was dried and nally annealed in Ar/H2 to obtain N-doped graphene/
graphite composite. The result shows that all of graphite particles was dispersed in three-dimensional
graphene framework with a rich of open pores. The open pore accelerates the electrolyte transport. The
graphene framework works as a conductive agent and graphite particle connector and improves the
electron transfer. Electrical conductivity of the composite reaches 5912 S m1, which is much better than
that of the pristine graphite (4018 S m1). The graphene framework also acts as an expansion absorber in
the anodes of lithium ion battery to relieve the large strains developed at high discharge rates. As a result,
the N-doped G/C electrode provides an excellent electrochemical performance for lithium ion battery,
including high specic capacity (781 mA h g1), outstanding rate capability (351 mA h g1 at 10 C) and
intriguing cycling stability (98.1% capacity retention at 10 C after 1000 cycles).
2015 Elsevier Ltd. All rights reserved.

Keywords:
graphite
graphene
composite
lithium ion battery
electrochemical performance

1. Introduction
Lithium ion battery has been widely used since its rst
commercialization by Sony Corporation in 1990s. It is also
considered as an attractive power source for electric vehicle
[13] and for stationary energy storage of solar and wind power
[4,5]. These applications have more demands for lithium ion
batteries in all aspect such as specic capacity, performance under
high charge/discharge rate, cycling stability, safety and cost. At
present, graphite plays a dominating role in eld of the anode
material in commercial lithium ion batteries owing to desirable
charge potential prole, good safety feature and low cost. However,
present graphite anodes can not provide high enough specic
capacity, cycle stability and rate capability. These greatly limit its
further development [6].
Two strategies have been used for the fabrication of graphite
anode materials to improve the electrochemical performance. One

* Corresponding author. Tel.: +86 13912371144.


E-mail address: zaijunli@263.net (L. Zaijun).
http://dx.doi.org/10.1016/j.electacta.2015.05.016
0013-4686/ 2015 Elsevier Ltd. All rights reserved.

is to reduce the particle size of graphite, especially nanoscale [7].


The nanostructured carbon is effective for improving lithium ion
insertion/extraction by providing large surface area, which is
benecial to the accommodation of additional lithium ions, and a
shorter path for lithium ion diffusion [8,9]. However, it also suffer
from a large irreversible capacity loss during the initial cycling, in
addition to the mass scalability of carbon material being
challenging. Another is to modify the surface of graphite particles
[10,11]. To date, amorphous carbon [12], carbon nanotube [13] and
graphite oxide [14] were used for the above aim. Amorphous
carbon has an isotropic feature different from graphite, which
enables lithium ions to transport inside randomly and thus
exhibits a good rate capability. Besides, amorphous carbon also
offers a minor volume change during the charge/discharge process
and good cyclic performance [15]. Many investigations have
demonstrated that the surface modication by coating amorphous
carbon is an effective approach to improve the electrochemical
performance. However, a proper coating layer is essential to
surface structure and electrochemical properties of the graphite.
An incomplete coating layer leads to the exposure of part of the
graphite surface, while excessive coating can cause a thick layer.

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

This leads to increase the diffusion distance of lithium ions and


affect the rate capability. Wang et al. studied the effect of coating
amount of glucose on the surface structure and the electrochemical properties [16]. The result shows that the sample coated with
5 wt.% glucose exhibits the highest reversible specic capacity,
excellent rate capability, and good cyclic performance. Since the
discovery of carbon nanotube, its applications to energy storage
devices have been highly issued. Compared with amorphous
carbon, carbon nanotube provides a shorter diffusion path for the
electron transfer, larger surface area and faster electronic/thermal
conductions. Moreover, carbon nanotube can also entangle with
particles to form an interconnected network, which is easier for
electrons to distribute and transport between particles [17]. Lee
et al. used carbon nanotube as a functional additive on the C-rate
capabilities of composite anodes [18]. The additive was observed to
act as a particle connector or an expansion absorber in the anodes
of lithium-ion batteries. By controlling the dispersion process,
carbon nanotube bundles were divided and dispersed between
host particles. The rounded graphite with 2.0 wt.% of carbon
nanotube exhibited a high rate capacity even at high electrode
density. In addition, the well-dispersed carbon nanotube bundles
enabled to relieve the large strains developed at high discharge
rates and to keep the electrical contact between the host particles
during repeated intercalation/deintercalation. However, the surface modication of graphite with amorphous carbon or carbon
nanotube does not substantially increase the specic capacity of
graphite anode materials. Graphene is a single atomic layer of
carbon connected by sp2-hybridized bonds and attracted strong
scientic interest since its recent discovery [19]. It has been
recognized as the most promising electrode material for lithium
ion battery due to superior electrical conductivity, high surface
area, and wide electrochemical window [20]. The researches have
proved that the specic capacity of graphene anode for lithium ion
battery can exceed 1000 mA h g1, which is about 3-fold that of the
graphite electrode [21]. However, the capacity will rapidly decay
with the increase of cycle number due to its graphitization. The
problems can be effectively solved by the introduction of other
particles in the graphene layers. Gu et al. developed a graphite/
graphene oxide composite as the anode material of lithium ion
battery [22]. The composite has more than 690 mA h g1 reversible
capacity at the rate of 0.5C, simultaneously with excellent cycle
performance and rate capability. However, the results of previous
researches has proved that graphene oxide is not very suitable to
be used as electrode materials for lithium batteries. On the one
hand, graphene oxide is an insulating material. Its poor electrical
conductivity brings a low high-rate capability. Its use need to add a
large amounts of conductive agent to improve the electrical
conductivity. This will increase the mass and volume of the
electrode material and thus limits its many applications in high
powder batteries. On the other hand, graphene oxide contains rich
of active groups such as hydroxyl, carboxyl and epoxy groups. The
combination of active groups with lithium ions will produce an
irreversible capacitance and thus leads to large reversible
capacitance loss. Moreover, the decomposition of active groups
in graphene oxide inevitable forms some free water during the
repeated charge/discharge process. This will bring a decline in
electrochemical performance [23,24].
In the study, we reported a new strategy for the synthesis of
N-doped graphene/graphite composite (termed as N-doped G/C).
The result shows that all of graphite particles was dispersed in
three-dimensional graphene framework with rich of open pores.
The unique structure creates ultrafast electron transfer and
electrolyte transport, and stable structure of the anode material.
The as-prepared N-doped G/C as conductive agent-free anode
material exhibits a greatly enhanced electrochemical performance
for lithium ion batteries.

157

2. Experimental
2.1. Synthesis of N-doped G/C
Graphite oxide (GO) (1.0 g) and urea (2.0 g) were dispersed in
ultra pure water (200 mL) by the ultrasonication. Followed by the
adding ascorbic acid (2.0 g) and the heating (90  C) for 1 h to form a
uniform and viscous solution. The solution was mixed with
graphite (6.7 g) by the mechanical stirring for 1 h and subsequently
treated by the hydrothermal reaction for 10 h under 160  C to
produce a graphene oxide/graphite gel. The gel was dried at 105  C
for 2 h and nally annealed at 400  C for 6 h in Ar/H2 atmosphere
(Ar:H2 = 95:5) to obtain the N-doped G/C composite. To determine
the amounts of graphene in the composite, two control samples,
including single graphite and single graphite oxide, were treated
by using the same procedure. According to the mass changes of
graphite and graphene oxide before and after treated, we can
calculate the content of graphene in the composite. The result
shows that the content of graphene in the as-prepared N-doped
G/C is 10.7%. To study on the effect of nitrogen doping and thermal
annealing on the electrochemical performance, the graphene/
graphite (G/C) and the N-doped graphene oxide/graphite (N-doped
GO/C) were also fabricated by using above method unless no
addition of urea or no use of the thermal annealing.
2.2. General characterization
Scanning electron microscope (SEM) was performed using
HITACHI S4800 with a X-ray Energy Dispersive Spectrometer (EDS)
(INCA Energy, Oxford Instruments). X-ray diffraction (XRD) was
measured on the D8 Advance with a Cu Ka radiation. Raman
measurements were carried out using InVia laser micro-Raman
spectrometer. X-ray photoelectron spectroscopy (XPS) was performed by PHI 5700 using Al KR radiation. N2 adsorption and
desorption isotherms were measured at 77 K on a Quantachrome
Nova 2000 and the CO2 isotherms were recorded at 273 K with a
Micromeritics TriStar 3000. Prior to the gas sorption measurements, all samples were outgassed in a vacuum at 120  C for 24 h.
The specic surface area and the pore size distribution were
calculated using the BraunauerEmmettTeller (BET) method, and
the relative pressure range of p/p0 from 0.1 to 0.3 was used for
multipoint BET calculations. Non-local density functional theory
(NLDFT) assuming the pores are slit/cylinder shaped was used to
determine the pore size distribution and mesopore volume.
Electrical conductivity measurement was carried out in a
ST-2258C multifunction digital four-probe tester, which equipped
with a SZT-D semiconductor powder resistivity tester (Suzhou
Jingge Electronic Co., Ltd. China). The powder sample was directly
placed in a round hole with the diameter of 5 mm on the SZT-D
semiconductor powder resistivity tester. Then, the powder was
slowly compressed to 100 atmospheres by the piston on the
system. At the same time, the electrical conductivity values under
different pressures were recorded.
2.3. Electrochemical measurement
Electrochemical properties of N-doped G/C, G/C and graphite
electrodes were evaluated using 2016 coin cells. The active
material was mixed with polyvinylidene uoride (PVDF, Sigma
Aldrich) at weight ratio of 9:1 in N-methylpyrrolidone (NMP,
SigmaAldrich) solvent to form uniform slurries, which were then
coated on copper foils. The loading density of active materials was
about 3.0 mg cm2. Subsequently dried in a vacuum oven at 120  C
overnight and rolled by using a rolling machine. The copper foil
was placed on the specialized slicing machine to prepare the
working electrode. These working electrodes were incorporated

158

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

into 2016 coin cells, in which Li foils were serviced as the counter
and reference electrode, Celgard 2400 as the separator, and a
mixed solvent of ethylene carbonate, dimethyl carbonate and
diethylene carbonate (1:1:1) containing of 1 M LiPF6 as the
electrolyte. The assembly process was conducted in an argonlled glove box having O2 and H2O contents below 0.1 ppm.
Discharge-charge tests were performed at a potential range of
0.012.0 V (vs. Li/Li+) on a CT2001A LAND Battery Test System. All
discharge-charge rates were denoted using the C-rate where
370 mA g1 was assigned to be current density of 1C based on
theoretical capacity of graphite (370 mA h g1). Cyclic voltammograms (CV) were performed in a CHI 660D Electrochemical
Workstation over the potential range of 0.012.0 V at a scanning
rate of 1 mV s1. Electrochemical impedance spectroscopy (EIS)
measurements were carried out on the coin cells using a CHI 660D
Electrochemical Workstation. A potential amplitude of 5 mV and
a frequency range of 0.01 to 105 Hz were adopted.
Electro-active area of the working electrode was estimated by
cyclic voltammograms at various scan rates. For a reversible
process, the Randles-Sevcik formula was used [25].
1=2

Ipa 260  105 n3=2 AC 0 DR v1=2


Here, Ipa, n, A, DR, C0 and v present the anodic peak current, the
number of electron transferred, the electro-active area (cm2) of
working electrode, the diffusion coefcient of Li+ (cm2 s1) in the
electrolyte solution, the bulk concentration of Li+ (mol cm3) in the
electrolyte and the scan rate of potential perturbation (V s1),
respectively. According to the equation, the electro-active areas of
N-doped G/C electrode and graphite electrodes were found to be
13.51 cm2 and 11.82 cm2, respectively.
3. Results and discussion
3.1. N-doped G/C synthesis
The synthesis of N-doped G/C includes three assemble
processes, i.e. the partly reduction of GO, mixing of GO with
graphite, and nitrogen doping of graphene (shown in Fig. 1). First,
graphite oxide and urea were dispersed in ultra pure water and
partly reduced by ascorbic acid to form a viscous GO dispersion.
Owing to the existence of big difference in the density between the
graphite and the GO dispersion, a simple mixing of graphite with
GO dispersion is difcult to form a stable dispersion by ordinary
mechanical stirring. Thus, one step for increasing GO viscosity is
strongly required prior to the mixing. An appropriate viscosity of
GO dispersion become a key factor to obtain good dispersion in the
nal product. Often, GO can be slowly reduced into graphene by
heating. The partly reduced GO sheets will self-assembly and
nally form GO hydrogel, which offers a relatively high viscosity. In
the step, we used ascorbic acid as a moderate reducing agent for
reducing GO. The result shows that the addition of ascorbic acid
remarkably speeds up the reaction rate, the color of GO dispersion
rapidly changes into black from yellow (shown in Fig. 2). Because of
the loss of some hydrophilic groups (hydroxyl, carboxyl and epoxy
groups), the partly reduced GO sheets have a lower watersolubility compared with pristine GO and results in an obvious

Fig. 2. Optical photographs of GO dispersion (a), GO dispersion partly reduced GO


by ascorbic acid (b), mixture of graphite and partly reduced GO (c) and GO/graphite
hydrogel (d).

increase in the viscosity. Moreover, urea can cross-link with GO


sheets by the chemical bonds and serves to increase the viscosity.
However, we also noted that graphite particles will be more
difcult to enter into the internal of the GO hydrogel structure
during the mixing process with the increase of the gelation degree.
When the heating time increases to 2.5 hours, the GO dispersion
will be completely changed into the GO hydrogel (see Fig. S1). In
this case, the addition of graphite into the system may not get a
good composite. The resulting product contains a relatively big
pieces and small powders (see Fig. S2). In order to determine the
types of the piece and the powder, the collected piece sample and
powder sample from the product were investigated by the SEMEDS analysis, respectively. The results in Fig. s3 exhibit that the
piece sample has rich of folds and porous structure, indicating
typical morphology features of graphene materials. The powder
sample is comprised of relatively big particles with smooth surface,
indicating typical morphology feature of graphite materials.
Further, the EDS analysis reveals that the piece sample contains
carbon (C), nitrogen (N) and oxygen (O) elements, which are
consistent with the composition of N-doped graphene. The powder
sample only contains carbon element, which is consistent with the
composition of graphite (shown in Fig. S4). The above results
demonstrate that an excessive gelation leads to produce a mixture
of N-doped graphene aerogel and graphite, in which the N-doped
graphene aerogel and graphite particles exist alone and are not
well mixed to form a good composite. This is because an excessive
gelation leads to form a large number of the solidied porous
structures. When the pore size is less than the particle size of
graphite, the graphite particle is difcult to enter into internal of
the hydrogel structure. In addition, the GO hydrogel will be broken
into a large number of small pieces of N-doped graphene aerogel
under agitating. For the reason, a strict control of the reaction
temperature and time was strongly required to obtain an optimal
gelation level.
The viscous GO solution was mixed with the amounts of
graphite under vigorous agitation. Followed by the hydrothermal

Fig. 1. The procedure for the preparation of N-doped G/C composite.

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

reaction to form a GO/graphite hydrogel. By mechanical stirring,


the high viscosity of GO dispersion make it rmly adhere to the
surface of graphite particles. As a result, the nal N-doped G/C
composite offers a relatively good dispersion. During the
hydrothermal reaction, these GO sheets will be further reduced
and result a higher gelation degree of GO. Because the most of
hydrophilic groups in the GO sheets were exfoliated, the GO/
graphite gel become insoluble in water and nally precipitated
from the system. Moreover, the volume of gel is largely compressed
under the high pressure and high temperature. The treatment
achieves to rmly block graphite particles in porous structure of
the gel, which reduces the distance between graphite and N-doped
graphene sheets. This is very important to improve the electrical
conductivity and tap density of the nal product.
The GO/graphite hydrogel was dried in air and nally annealed
in Ar/H2 to obtain a N-doped G/C composite. In this step, we need
to consider two key issues. One is how to keep three-dimensional
structure of graphene framework. Often, three-dimensional
structure of GO hydrogel will be completely destroyed during
the drying due to rapidly evaporation of water. For the reason,
many researchers have to adopt freeze-drying for the preparation
of GO aerogel. However, the process is time-consuming and
energy-consuming and difcult to be used in the industrial
production. In the study, the most of space in the hydrogel has been
occupied by graphite particles. The feature in structure allow us to
use a simple method to remove water from the hydrogel. The result
conrms that its high mechanical strength and three-dimensional
structure can be well maintained during the drying. Another is how
to achieve the best match of fast electron transfer and rapid
electrolyte transport for the composite electrode material. By
thermal annealing, the GO/graphite hydrogel was fully reduced
and formed a graphene/graphite aerogel. To evaluate the effect of
graphene on the electrical conductivity, a four-probe method was
employed for the electrical conductivity measurement of the
composite and graphite powder samples. Often, the electrical
conductivity of powder sample will increase with increase of the
pressure. The electrical conductivity lends to the constant when
exceeded a certain pressure. Our investigation shows that the
electrical conductivity can remain almost unchanged when the

159

pressure is more than 80 atmospheres for the composite and


graphite. Thus, the pressure of 100 atmospheres was selected for
the electrical conductivity measurement. The electrical conductivity of N-doped G/C composite was found to be 5912 S m1, which
is more than 1.4-fold that of pristine graphite (4018 S m1). This is
because graphene framework as a particle connector of graphite
greatly improves the electron transfer. In addition, the thermal
annealing also contributes to produce a very small gap between
graphite particles and graphene sheets owing to their difference in
thermal expansion coefcient [26]. This will further reduce the
blocking of graphene sheets on the electrolyte transport.
3.2. Structure characterization
The morphology and structure of N-doped G/C and graphite
were characterized by SEM-EDS. As shown in Fig. 3, pristine
graphite particles exhibit a smooth surface and clear edges and
corners, indicating a high crystallinity. There only is one carbon
peak on the EDS pattern of graphite, verifying that the graphite
sample has a high purity. The N-doped graphene framework is
present in the N-doped G/C composite, in which graphite particles
were dispersed in the framework. The selected region EDS analysis
proves that the framework are composed of carbon (C), nitrogen
(N) and oxygen (O) elements. The chemical composition is
different from that of pristine graphite and is consistent with
the composition of N-doped graphene, verifying that the
framework is composed of N-doped graphene. Owing to unique
electrical, mechanical and mechanical properties, such a N-doped
graphene framework can act as a particle connector to enhance the
electrical conductivity, and an expansion absorber in the anodes of
lithium ion battery to relieve the large strains developed at high
discharge C rates. The enlarged SEM images further reveals that the
surface of graphite particles was coated by the wrinkled graphene
sheets. The self-assembly of graphene sheets leads to form a threedimensional graphene framework with a rich of open porous
structure, which will improve the electrolyte transport. In order to
well understand the structure of graphene framework, a control
sample (termed as graphene aerogel) was prepared by the same
procedure unless no addition of graphite. Fig. S5 indicates that all

Fig. 3. The SEM images of graphite (a) and N-doped G/C (b) and enlarged SEM of N-doped G/C (c) and EDS patterns of graphite and N-doped graphene(d).

160

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

of graphene sheets was intertwined each other to form a graphene


aerogel. The aerogel shows a three-dimensional structure with
well-dened porous distribution. The macropores provides sufcient space for the entry of graphite particles for the hybridization
of graphene oxide with graphite. The meso- and micropores will be
served as the channel for fast electrolyte transport. The result also
conrms that a 3D graphene gel can be formed during the
synthesis of N-doped G/C composite.
Fig. 4 presents typical nitrogen adsorption/desorption isothermal curves and pore size distribution of the N-doped G/C. The type
IV nitrogen adsorption/desorption isothermal curves offer a
hysteresis loop at high relative pressure. The fact demonstrates
the existence of plentiful mesopores in the composite. The pore
size distribution exhibits one sharp peak at 2.8 nm and one broad
peak at 12 nm. The broad pore size distribution, spanning from
several to 100 nm, implies that the composite is rich in the
hierarchical pores. The macropores could originate from the
interconnected hollow space, the micro- and mesopores could be
generated by the wrinkled morphology of graphene sheets.
Moreover, we also noted that BET surface area of the as-prepared
N-doped G/C reaches 25.6 m2 g1. The value is more than that of the
pristine graphite (4.2 m2 g1), indicating that the introduction of
graphene aerogel increases the specic area. This is because the
graphene aerogel provides a bigger BET surface area when
compared with the pristine [27].
XPS technology was applied to measure the element type and
chemical state of N-doped G/C. Fig. 5 shows that total XPS
spectrum offers four peaks at 284.58, 531.64, 399.71 and 169.34 eV,
respectively. The result shows that the samples contains carbon
(C), oxygen (O), nitrogen (N) and sulfur (S) elements. The C1s XPS
spectrum indicates four peaks at 284.6, 285, 286.6 and 288.1 eV,
respectively. The peaks at 284.4, 286.6 and 288.1 eV are assigned to
CC, C
O and CO species respectively [28]. The XPS peak at
285 eV is assigned to sp2 C bonded to N. The N1s XPS spectrum has
three peaks at 398.4, 399.8 and 401 eV, respectively. The peak at
398.4 eV can be assigned to N2, corresponding to pyridinic N. The
peak at 399.8 eV is assigned to amide, amine or pyrrolic N. The peak
at 401 eV can be assigned to N4, corresponding to graphitic N. This
reveals that nitrogen replaced carbon in graphene sheets and was
incorporated into the carbon network [29]. Moreover, we also
noted that the peak intensity of amide nitrogen was obviously
stronger than that of pyridinic nitrogen and graphitic nitrogen,
implying that amide nitrogen was dominant in the as-prepared
materials. Because pyridinic nitrogen and pyrrolic nitrogen are
located at the edge of the carbon materials, which will induce more
disorders of the nal carbon materials and leads to produce a broad

D band in the Raman spectrum. These results demonstrates that


we have successfully achieved nitrogen doping by the thermal
annealing.
The pristine graphite and N-doped G/C samples were subjected
to XRD and Raman measurement to evaluate the effect of
graphene. Fig. 6A shows that two samples exhibit a very similar
XRD patterns. The main peaks of 2u at 26.42 , 44.52 , and 54.52
can be indexed to a typical hexagonal graphite structure (JCPDF no.
41-1487). This demonstrates that the hybridization process of
graphite with graphene did not destroy the crystal structure of
graphite. However, we also noted that the N-doped G/C gives a
higher diffraction intensity than the pristine graphite. The increase
in crystallinity might imply that a small change on the surface
morphology of graphite takes place, i.e., the graphene surface layer
is formed. Fig. 6B presents typical Raman spectra of graphite,
graphene and N-doped G/C. Often, Raman spectrum of graphene is
characterized by two main features: G band arising from the rst
order scattering of E1g phonon of sp2 carbon atoms and D band
arising from a breathing mode of point photons of A1g symmetry.
The most of carbon in the graphite exists as sp2 carbon, thus its
Raman spectrum offers the highest G band and the smallest D band
among three samples. However, carbon atoms in the edge of
graphene sheets are changed into sp3 carbon during the oxidation
process. This will result in an obvious decrease of G band and the
increase of D band. From Fig. 6B, we can calculate the R value (the
intensity ratio of D band and G band) of the each of carbon
materials. The result shows that the R value of N-doped G/C (0.54)
is greater than that of pristine graphite (0.052) while less than that
of graphene (0.83). The result again demonstrates that the
as-prepared N-doped G/C is the mixture of graphite and graphene.
3.3. Electrochemical property
Fig. 7 shows the cyclic voltammograms (CVs) of N-doped G/C
electrode and graphite electrode from 0 V to 2.0 V. Two kinds of
electrodes offer a very similar shape of CV curve. The each CV curve
can be analyzed into two sections. One section from 0.5 V to 2.0 V is
corresponding to the formation of SEI lm on the interfere
between the electrode and the electrolyte [30]. Because the
formation of SEI lm leads to some fading of active sites, the peak
area of CV from 0.5 V to 0.0 V in the second cycle is obviously less
than that in the rst one. Moreover, we also nd that the reducing
peak potential of N-doped G/C electrode can remain almost
unchanged in two cycles. This is because the graphite surfaces in
the N-doped G/C are well coated by graphene sheets. This will
effectively inhibit the formation of the SEI lm and improves the

Fig. 4. Nitrogen adsorption/desorption isotherm (A) and pore-size distribution curve for N2 (B) of the N-doped G/C.

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

120000

161

70000

Total

C1s
C1s

100000

C-C

60000

50000

C-N

Counts (a.u)

Counts (s)

80000

60000

N1s

40000

O1s

40000

30000

20000

C-O

20000
10000

S2p
0

C=O

0
0

200

400

600

800

1000

280

283

Binding energy (eV)

286

289

292

295

Binding energy (eV)

6000

7000

O1s

N1s

O-C

6000

5000

Counts (s)

Counts (s)

5000

4000

4000

3000

3000

O=C

2000
2000

1000

1000

0
395

398

401

404

407

410

525

528

531

534

537

540

Binding energy (eV)

Binding energy (eV)

Fig. 5. Total, C1s, N1s and O1s XPS spectra of the N-doped G/C.

20000

1500

A
16000

1200

N-doped G/C
Intensity (a.u)

Intensity (a.u)

graphite
900

600

12000

8000

graphene

4000

300

graphite

N-doped G/C
0

0
10

20

30

40

50

60

70

500

1000

2 (degree)

1500

2000

Raman shift (nm)


Fig. 6. XRD pattern (A) and Raman spectra (B).

2500

3000

162

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

15

15

A
10

Current (mA cm-2)

Current (mA cm-2)

10

first/second-cylce

-5

-10

first/second-cycle
0

-5

-10

-15
0

0.4

0.8

1.2

1.6

-15
0

Potential (V)

0.4

0.8

1.2

1.6

Potential (V)

Fig. 7. CV curves of N-doped G/C electrode (A) and graphite electrode (B) at 0.1 mV/s.

electrochemical performance. However, the reducing peak potential of graphite electrode increases from 0.07 V to 0.1 V, indicating a
relatively poor electrical conductivity. Another section from 0.0C
and 0.5 V is corresponding to Li+ intercalation/deintercalation
process. Fig. 7 shows that the CV curve of each electrode gives a
pair reversible oxidation/reduction peak in the second section of
CV each curve. The peak potential of N-doped G/C is similar with
corresponding graphite electrode, verifying that the introduction
of graphene does not change the electrochemical process of
graphite material. However, the N-doped G/C electrode shows a
lower peak potential and higher peak current when compared with
graphite electrode, indicating a faster Li+ intercalation/deintercalation process. These improved CV performances are attributed
that the introduction of graphene enhances the electrical
conductivity and the formed SEI lm.
Fig. 8 shows typical impedance spectra of N-doped G/C and
graphite electrodes in the fully discharged state after the rst,
second and ftieth cycles at 0.2C rate. For the each of electrodes,
the overall shape of Nyquist plot is composed of a depressed
semicircle at high frequency region and a straight line at low
frequency region. The intercept of the depressed semicircle at
high-frequency region on the real axis can be assigned to the total
interfacial resistance, which consists of the resistance of charge

transfer at the solid lm interface and the resistance of Li+


migration through SEI lm [31]. The straight line is attributed to
the diffusion of the Li+ into the bulk of the electrode material [32].
Fig. 8 shows that total interfacial resistance of the electrode in the
second cycle are smaller than that in the rst cycle, verifying that
the formed SEI lm improves the electrical conductivity. However,
total interfacial resistance in the ftieth cycle is slightly smaller
that in the second cycle, indicating high stability of the SEI lm. An
equivalent circuit of the impedance spectra is presented in the
inset in Fig. 8, which Rs, Rf and Rct, are denote the solution
resistance, the contact resistance and the charge-transfer resistance, respectively [33]. The parameters and the diffusion
coefcient of Li+ (D) in the ftieth cycle are calculated by using
a reported method [34]. Table 1 indicates that the N-doped G/C
offers a lower Rct value and a larger Li+ diffusion coefcient
compared with he graphite. This demonstrates that the presence of
Table 1
Impedance parameters of the graphite and N-doped G/C electrodes after 50 cycles
at 0.2C in 25  C
Anode material

Rs (V)

Rf (V)

Rct (V)

D (cm2 s1)

Graphite
N-doped G/C

133.1
26.5

1644.2
28.0

4234.5
134.4

4.24  1016
6.01 1012

Fig. 8. AC impedance spectra of N-doped G/C electrode (A) and graphite electrode (B) with the equivalent circuit from the EIS measurements (inset).

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

163

graphene can signicantly suppress the rise of both of the surface


lm resistance and the charge transfer resistance, which will
improve the Li+ diffusion in the SEI lm and the bulk electrode
materials.
3.4. Cell performance
Fig. 9 shows the charge/discharge curves of N-doped G/C, G/C
and graphite electrodes at a potential range of 0.02.0 V with
different rate from 0.1 C to 10 C. It can be seen that the N-doped G/C
electrode exhibits the highest specic capacity at the each of rates
among four electrodes. Its discharge capacity reaches 781 mA h g1
at 0.1 C, which is more than 2-fold that of theoretical capacity of
graphite electrode (372 mA h g1). The enhanced capacity is
attributed to the introduction of N-doped graphene, because the
specic capacity of graphene can excess 1500 mA h g1 for lithium
ion batteries [34]. The capacity will reduces to 737 mA h g1 after a
ve cycles. The reduced capacity mainly originates from some
fading of active sites on the electrode due to the formation of SEI
lm. The reversible capacity can remain 351 mA h g1 at 10 C,
indicating an excellent rate capability. This is because the
introduction of N-doped graphene enhances the electrical
conductivity of electrode material and SEI lm, which enhances
the rate capability. In the study, N-doped GO/C was used as a
control sample to examine the effect of thermal annealing. Fig. 9
shows that the N-doped GO/C electrode can only provide a slightly
bigger specic capacity at all charge/discharge rate when
compared with the graphite electrode, which is largely smaller
than that of the N-doped G/C and G/C electrodes. The result
demonstrates that the thermal annealing is very important to
improve the electrochemical performance. On the one hand, a
relatively large number of active groups in the N-doped GO/C can
combine with Li+ to form stable compound during the charge
process. This will bring a high irreversible capacity and the
decrease of reversible capacity. On the other hand, its poor
electrical conductivity will lead to a poor rate capacity. Moreover,
the graphene oxide sheets in N-doped GO/C tightly wrapped on the
surface of graphite particles. This partly blocks the electrolyte
transport and results in the decrease of specic capacity, especially
specic capacity at high rate. In the study, the G/C sample was used
as a control to evaluate the effect of nitrogen doping. Fig. 9 shows
that the G/C electrode provides a lower specic capacity at the each

Fig. 10. Cyclic performance of N-doped G/C electrode at 10 C.

of all rate when compared with the N-doped G/C electrode. The
result conrms that the nitrogen doping plays an important role in
the improvement of cell performance. The introduction of nitrogen
atom in the graphene sheet increases the polarity of graphene
material due to its big electronegativity, and destroy some planar
structure of graphene sheets owing to its sp3 nitrogen atom. These
are benecial to improve mass transport of the electrolyte and
results in an enhanced electrochemical performance.
The cyclic performance is very important to practical application of electrode materials for lithium ion batteries. Fig. 10 presents
continual galvanostatic charge/discharge 1000 tests for the
N-doped G/C electrode with potential window of 0.02.0 V at
10 C. The discharge capacity was 365 mA h g1 in the rst cycle.
The capacity can remain 359 mA h g1 after 1000 charge/discharge
cycles. The capacity loss is about 2%, indicating an excellent
cycle stability. This is attributed that the graphene framework in
the composite acts as an expansion absorber in the anodes of
lithium ion battery to relieve the large strains developed at high
discharge C rates. This is benecial to keep electrical contact
between the host particles during the repeated intercalation/
deintercalation.
4. Conclusions
We have demonstrated the fabrication of N-doped graphene/
graphite anode material for lithium ion batteries. Since threedimensional N-doped graphene framework greatly improves
electrical conductivity of the electrode material, mass transport
of the electrolyte and structure stability of the electrode, the Ndoped graphene/graphite electrode exhibits an enhanced electrochemical performance for lithium ion batteries. The study also
provides an attractive approach for building on the graphite-based
anode materials for high power storage devices.
Acknowledgements

Fig. 9. Charge/discharge curves of N-doped G/C, G/C, N-doped GO/C and graphite
electrodes at various discharge rate (from under to down).

The authors acknowledge the nancial support from Prospective Joint Research Project: Cooperative Innovation Fund (No.
BY2014023-01), the country 12th Five-Year Plan to support
science and technology project (No. 2012BAK08B01), National
Natural Science Foundation of China (No. 21176101), Fundamental
Research Funds for Central Universities (No. JUSRP51314B) and
MOE & SAFEA for the 111 Project (B13025).

164

W. Guanghui et al. / Electrochimica Acta 171 (2015) 156164

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.
electacta.2015.05.016.
References
[1] Y.S. Choi, D.M. Kang, Prediction of thermal behaviors of an air-cooled lithiumion battery system for hybrid electric vehicles, J. Power Sources 270 (2014)
273280.
[2] L.H. Saw, Y. Ye, A.A.O. Tay, Electro-thermal analysis and integration issues of
lithium ion battery for electric vehicles, Appl. Energy 131 (2014) 97107.
[3] N. Takami, H. Inagaki, Y. Tatebayashi, H. Saruwatari, K. Honda, S. Egusa, Highpower and long-life lithium-ion batteries using lithium titanium oxide anode
for automotive and stationary power applications, J. Power Sources 244 (2013)
469475.
[4] T.L. Gibson, N.A. Kelly, Solar photovoltaic charging of lithium-ion batteries, J.
Power Sources 195 (2010) 39283932.
[5] A. Purvins, M. Sumner, Optimal management of stationary lithium-ion battery
system in electricity distribution grids, J. Power Sources 242 (2013)
742755.
[6] N.C. Gallego, C.I. Contescu, H.M. Meyer III, J.Y. Howe, R.A. Meisner, E. Andrew
Payzant, M.J. Lance, S.Y. Yoon, M. Denlinger, D.L. Wood III, Advanced surface
and microstructural characterization of natural graphite anodes for lithium
ion batteries, Carbon 72 (2014) 393401.
[7] K.J. Kim, T.S. Lee, H.G. Kim, S.H. Lim, S.M. Lee, A hard carbon/microcrystalline
graphite/carbon composite with a core-shell structure as novel anode
materials for lithium-ion batteries, Electrochim. Acta 135 (2014) 2734.
[8] B.B. Wu, T. Liu, Q.B. Xia, Hard carbon with nano-graphite domain as high
performance anode material for lithium-ion batteries, J. Electrochem. Soc. 160
(2013) A1720A1724.
[9] S.K. Kim, B.J. Shin, J.H. Kim, S. Ahn, S.Y. Lee, Nano-encapsulation of graphitebased anodes by a novel polymer electrolyte and its inuence on C-rate
performances of Li-ion batteries, Electrochem. Commun. 10 (2008)
16251628.
[10] F. Ding, W. Xu, D. Choi, W. Wang, X.L. Li, M.H. Engelhard, X.L. Chen, Z.G. Yang, J.
G. Zhang, Enhanced performance of graphite anode materials by AlF3 coating
for lithium-ion batteries, J. Mater. Chem. 22 (2012) 1274512751.
[11] T. Placke, V. Siozios, R. Schmitz, S.F. Lux, P. Bieker, C. Colle, H.-W. Meyer, S.
Passerini, M. Winter, Inuence of graphite surface modications on the ratio of
basal plane to non-basal plane surface area and on the anode performance in
lithium ion batteries, J. Power Sources 200 (2012) 8391.
[12] Q. Wang, H. Li, L.Q. Chen, X.J. Huang, Novel spherical microporous carbon as
anode material for Li-ion batteries, Solid State Ionics 152153 (2002) 4350.
[13] Y. Nomura, I.V. Anoshkin, C. Okuda, M. Iijima, Y. Ukyo, H. Kamiya, A.G.
Nasibulin, E.I. Kauppinen, Carbon nanotube/nanobers and graphite hybrids
for Li-Ion battery, J. nanometer. 2014 (2014) 586241-1586241-7.
[14] V.S. Channu, R. Bobba, R. Holze, Graphite and graphene oxide electrodes for
lithium ion batteries, Colloids and Surfaces, Colloid Surf. A-Physicochem. Eng.
Asp. 436 (2013) 245251.
[15] L.W. Ji, Z. Lin, M. Alcoutlabi, X.W. Zhang, Recent developments in
nanostructured anode materials for rechargeable lithium-ion batteries,
Energy Environ. Sci. 4 (2011) 26822699.
[16] C.M. Wang, H.L. Zhao, J. Wang, J. Wang, P.P. Lv, Electrochemical performance of
modied articial graphite as anode material for lithium ion batteries, Ionics
19 (2013) 221226.

[17] X. Zheng, K.Q. Wu, J.L. Mao, X.X. Jiang, L.Y. Shao, X.T. Lin, P. Li, M. Shui, J. Shu,
Improved electrochemical property of copper nitrate hydrate by multi-wall
carbon nanotube, Electrochim. Acta 147 (2014) 765772.
[18] S.Y. Lee, J.H. Park, P. Park, J.H. Kim, S. Ahn, K.J. Lee, H.D. Lee, J.S. Park, D.H. Kim, Y.
U. Jeong, Effect of MWCNT on the performances of the rounded shape natural
graphite as anode material for lithium-ion batteries, J. Solid State Electrochem.
14 (2010) 951956.
[19] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V.
Grigorieva, A.A. Firsov, Electric eld effect in atomically thin carbon lms,
Science 306 (2004) 666669.
[20] A. Kumar, A.L. Mohana Reddy, A. Mukherjee, M. Dubey, X.B. Zhan, N. Singh, N.
Singh, L.J. Ci, W. Edward Billups, J. Nagurny, G. Mital, P.M. Ajayan, Direct
synthesis of lithium-intercalated graphene for electrochemical energy storage
application, ACS Nano 5 (2011) 43454349.
[21] V.S. Channu, R. Bobba, R. Holze, Graphite and graphene oxide electrodes for
lithium ion batteries, Colloid Surf. A-Physicochem. Eng. Asp. 436 (2013)
245251.
[22] J.X. Zhang, H.Q. Cao, X.L. Tang, W.F. Fan, G.C. Peng, M.Z. Qu, Graphite/graphene
oxide composite as high capacity and binder-free anode material for lithium
ion batteries, J. Power Sources 241 (2013) 619626.
[23] L.H. Zhuo, Y.Q. Wu, W. Zhou, L.Y. Wang, Y.C. Yu, X.B. Zhang, F.Y. Zhao, Trace
amounts of water-induced distinct growth behaviors of NiO nanostructures on
graphene in CO2-expanded ethanol and their applications in lithium-ion
batteries, ACS Appl. Mater. Interfaces 5 (2013) 70657071.
[24] L.Q. Zheng, S.J. Li, H.J. Lin, Y.Y. Miao, L. Zhu, Z.J. Zhang, S.J. Li, H.J. Lin, Y.Y. Miao, L.
Zhu, Z.J. Zhang, Effects of water contamination on the electrical properties of
18650 lithium-ion batteries, Russ. J. Electrochem+ 50 (2014) 904907.
[25] N. Nasirizadeh, H.R. Zare, A.R. Fakhari, H. Ahmar, M.R. Ahmadzadeh, A. Naeimi,
A study of the electrochemical behavior of an oxadiazole derivative
electrodeposited on multi-wall carbon nanotube-modied electrode and its
applicationas a hydrazine sensor, J.Solid State Electrochem. 15 (2011)
26832693.
[26] L.W. Fan, J.M. Khodadadi, A theoretical and experimental investigation of
unidirectional freezing of nanoparticle-enhanced phase change materials, J.
Heat. Trans-T. Asme 134 (2012) 092301.
[27] J.J. Zhang, R.Y. Li, Z.J. Li, J.K. Liu, Z.G. Gu, G.L. Wang, Synthesis of nitrogen-doped
activated graphene aerogel/gold nanoparticles and its application for
electrochemical detection of hydroquinone and o-dihydroxybenzene,
Nanoscale 6 (2014) 54585466.
[28] Z.G. Mou, X.Y. Chen, Y.K. Du, X.M. Wang, P. Yang, S.D. Wang, Forming
mechanism of nitrogen doped graphene prepared by thermal solid-state
reaction of graphite oxide and urea, Appl. Surf. Sci. 258 (2011) 17041710.
[29] S. Yasuda, L. Yu, J. Kim, K. Murakoshi, Selective nitrogen doping in graphene for
oxygen reduction reactions, Chem. Commun. 49 (2013) 96279629.
[30] S.L. Chou, Y. Zhao, J.Z. Wang, Z.X. Chen, H.K. Liu, S.X. Dou, Silicon/single-walled
carbon nanotube composite paper as a exible anode material for lithium ion
batteries, J. Phys. Chem. C114 (2010) 1586215867.
[31] H. Buqa, A. Wrsig, J. Vetter, M. Spahr, F. Krumeich, P. Novk, SEI lm formation
on highly crystalline graphitic materials in lithium-ion batteries, J. Power
Sources 153 (2006) 385390.
[32] J. Liu, R. Jiang, X. Wang, T. Huang, A. Yu, The defect chemistry of LiFePO4
prepared by hydrothermal method at different pH values, J. Power Sources 194
(2009) 536540.
[33] J. Yao, F. Wu, X. Qiu, N. Li, Y. Su, Effect of CeO2-coating on the electrochemical
performances of LiFePO4/C cathode material, Electrochim. Acta 56 (2011)
55875592.
[34] Y. Cui, X. Zhao, R. Guo, High rate electrochemical performances of nanosized
ZnO and carbon co-coated LiFePO4 cathode, Mater. Res. Bull. 45 (2010)
844849.