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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
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
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
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
159
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
Fig. 4. Nitrogen adsorption/desorption isotherm (A) and pore-size distribution curve for N2 (B) of the N-doped G/C.
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
286
289
292
295
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
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
2500
3000
162
15
15
A
10
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
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).
163
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
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