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Facile synthesis of graphene-titanium dioxide

nanocomposites as anode materials for Na-ion
batteries
Jian-Min Feng, Lei Dong, Yan Han, Xi-Fei Li*, De-Jun Li**
Energy & Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin
300387, China

article info

abstract

Article history:

Graphene-titanium dioxide (TiO2) materials were prepared using titanium tetrachloride

Received 6 February 2015

(TiCl4) and graphite oxides (GO) via a simple and continuous vapor reaction process. TiO2

Received in revised form

nanoparticles obtained from the reaction assembled into clusters loading on graphene or

27 October 2015

attached onto graphene individually to form graphene-TiO2 nanocomposites. Graphene

Accepted 29 October 2015

not only could enhance the nanocomposite electric conductivity but also is useful to

Available online 21 November 2015

improve the material porosity. The nanocomposites exhibited an enhanced performance

for Na-ion battery anode with a specific capacity of 115 mAhg
1 at a current of 1 A/g and a

Keywords:

stable specific capacity of 102 mAhg
1 at 0.1 A/g after 300 cycles.

Graphene

Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

TiO2
Anode
Na-ion batteries
Cycling performance

Introduction
Currently, increasing demand of green energy drives a pursit
for high performance and cost-effective energy storage system. Li-ion battery system has received lots of interests, the
excellent performance and stable product process have been
achieved, however, there will be a limitation in the face of
future large-scale application considering Li resource scarcity.
Aiming at this, Na-ion battery based on rich and low-cost of
Na resource has been put forwarded, which was regarded as a
low-cost alternative for green energy storage, including solar
energy, wind energy and etc.

The working mechanism of Na-ion battery is the same as

that of Li-ion battery, both of which based on ion rockingchair intercalationedeintercalation processes. The different
is that the ionic radius of Na-ion is 1.02 
A, which is bigger than
that of Li-ion about 1/4. The bigger Na-ion not only leads to the
difficulties of ion embedding into electrode materials, but also
the expansion damage and poor cyclic stability [1]. Therefore,
to develop new Na-ion battery anode materials is one of the
most crucial challenges for the application of Na-ion battery.
So far, the developed anode materials of Na-ion battery
include hard carbons [2,3], alloying materials such as Sn [4e9],
Cu6Sn5 [10], NiSn [11], Sb [12,13], NiP3 [14], etc. However, the

* Corresponding author. Tel./fax: 86 22 23766505.

** Corresponding author. Tel./fax: 86 22 23766505.
E-mail addresses: xfli2011@hotmail.com (X.-F. Li), dli1961@163.com (D.-J. Li).
http://dx.doi.org/10.1016/j.ijhydene.2015.10.137
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

356

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 3 5 5 e3 6 0

cyclic stability of the materials above for Na-ion battery does

not still satisfy the practical application.
Titanium dioxide (TiO2) has been proved to be a stable and
low-cost electrode materials for Li-ion anode materials.
Recently, considering with TiO2 smooth channel for ion
intercalationedeintercalation and low-cost, the research of
TiO2 for Na-ion battery has also been attracted intersets, such
as TiO2 nanotube [15,16], anatase TiO2 nanorod [17], anatase
TiO2 nanoparticle [18] and TiO2(B) nanoparticle [19]. More
importantly, due to the poor electric conductivity of TiO2, that
is a limit factor for ratio capability when TiO2 used for battery.
Combining conductive nano-carbon with TiO2 to material
electric conductivity has been proved an effective method in
previous works for Li-ion battery [20]. Recently, the porous
carbon/TiO2 [21,22] and N-doped porous graphene/TiO2 [23]
have also been used for Na-ion battery.
At present, we developed a vapor reaction process to prepare graphene-TiO2 for Na-ion battery with a purpose to find a
low-cost and simple electrode material preparation process.
Titanium tetrachloride (TiCl4), the normal raw materials for
TiO2 industrial production, was used as titanium source,
which was carried into the reaction using argon flow through
a bubble method. GO was dispersed in water, and injected into
the reaction. TiCl4, GO, and water reacted in a quartz tube at
850  C and obtained graphene-TiO2 in one-step (Fig. 1). The
materials for Na-ion battery anode materials have shown a
good cycle stability and ratio performance. The stable
discharge specific capacity is 102 mAhg
1 at 0.1 A/g and ratio
test specific capacity is 115 mAhg
1. The utilization ratio of
Na-ion storage ability of TiO2 in the nanocomposites from this
simple vapor reaction process is comparable with the previous reports [18,23].

Experimental
The fabrication of graphene-TiO2 dioxide materials was performed in a quartz tube (60 cm in length and 6 cm in diameter)
placed in a horizontal electrical furnace (40 cm in length). Prior
to the reaction, the titanium source of TiCl4 (50 mL) was
extracted from the reagent bottle using an injector. The
extracted titanium source was then injected into a sealed
bottle. The sealed bottle was first connected to the quartz tube
sealing flange through a steel tube, and the quartz tube was
then sealed using two sealing flanges on both ends (Fig. 1).
After 200 sccm argon flow was poured into the quartz tube for
1 h, the quartz tube was heated to 850  C, whereas the TiCl4 in
the bottle was heated to 40  C 1  C through water bath

heating. The precusor of graphene from GO, which was prepared using the Hummer method (0.5 g), was added to the
deionized water (200 mL) and then ultrasonicated for 20 min
until a black ink-like GO aqueous solution was obtained. The
solution was then placed in an injector. TiCl4 vapor was carried into the reaction using 1000 sccm argon flow through a
bubble method. The GO aqueous solution was injected into
the argon flow at 10 mL/h and then carried into the reaction.
The reaction time was 45 min. Pure TiO2 and graphene were
also prepared for comparison, which was prepared from TiCl4
and H2O and GO using the same process as that for grapheneTiO2.
The morphologies and structures of the as-prepared materials were characterized by scanning electron microscopy
(SEM, TDCLS-4800, Hitachi, Japan) and transmission electron
microscopy (TEM, Tecnai G2 F20, Philips, Holland). The phases
of the samples were determined using X-ray diffraction (XRD,
Rigaku D/max 2500 v/pc, Tokyo, Japan). The specific area and
pore structure of graphene-TiO2 and TiO2 were analyzed
through the BrunauereEmmetteTeller method (NOVA2000,
Quantachrome, USA) using 200 mg of the samples. The content of TiO2 in graphene-TiO2 was evaluated by thermal
gravimetric analysis (TGA, TGA/DSC1/1100, METTLER, Germany) in a 15 sccm air flow at a heating rate of 10  C/min using
15 mg samples.
The as-prepared graphene-TiO2 materials were used as
anode electrode materials and were assembled into Na-ion
batteries for electrochemical measurements. The materials
were mixed with acetylene black powder as a conductor and
polyvinylidene fluoride as a binder at a weight ratio percentage (wt.%) of 85:10:5. The mixture was then dipped in Nmethyl-2-pyrrolidone and mechanically grinded to form a
slurry. The slurry was paste on a piece of Cu foil, dried for 24 h
at 80  C, and cut into 9 mm-diameter circular disc electrodes.
The load of corresponding active material (mg/cm2) in the disc
working electrodes is 0.6e0.8 mg/cm2.
The electrode was assembled into a battery in a glove box,
Na foil as counter and reference electrodes, 1 mol/L NaPF6 in
ethylene carbonate and dimethyl carbonate (3:7 by volume)
adding with 5% fluoroethylene carbonate as electrolytes, and
Whatman GF/C borosilicate glassfiber film as separators.
Galvanostatic chargeedischarge cycle tests were performed
on a battery testing system (LAND 2001A, Wuhan Jinnuo,
China) at a current density of 50e1500 mAhg
1 and a potential
range of 0 Ve3.0 V vs. Na/Na
. The discharge and charge
capacities of the graphene-TiO2 anode in absolute (mAh) and
weight-normalized values (mAhg
1) were automatically
generated from the measuring system. The cyclic voltammetry test for Na-ion battery was also conducted (VersaSTAT4,
Princeton Instruments, American).

Results and discussion

Fig. 1 e Diagram of the preparation of graphene-TiO2 by

vapor reaction process.

Graphene-TiO2 materials were prepared using the vapor reaction process. Fig. 2a shows the XRD patterns of the materials. The peaks at 25.2 , 37.8 , 48.0 , 53.9 , 55.0 , 62.6 , 68.7 ,
70.1 , 75.0 , and 82.6 correspond to the reflections of the (101),
(004), (200), (105), (211), (204), (116), (220), and (215) crystal
planes of anatase TiO2, respectively. No peak corresponding to

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357

Fig. 2 e XRD patterns of graphene-TiO2, TiO2, GO, and graphite (a) and N2 adsorptionedesorption isotherms of grapheneTiO2 and TiO2 (b).

the rutile phase was observed. In comparison, the XRD pattern

of the pure TiO2 had two peaks, one corresponding to anatase
and the other corresponding to rutile. It indicates that the
phases of TiO2 in the graphene-TiO2 materials differed from
the pure TiO2 material. The difference may result from the
presence of graphene in the materials. Graphene may play a
similar inhibitory role in the phase transformation of TiO2
from anatase to rutile, as that of carbon nanotubes previously
reported [24]. The XRD pattern of graphene-TiO2 materials
showed no obvious peak corresponding to the (001) plane
(11.7 ) of GO. Thus, the GO was completely reduced to
graphene.
The existence of graphene could improve the porosity of
materials. Fig. 2b shows the N2 adsorptionedesorption isotherms of the materials and the reference pure TiO2. The
specific surface area of the nanocomposites is calculated to be
28 m2/g, which is three times larger than that of the pure TiO2
(7 m2/g). The absorptionedesorption isotherms of the materials are closed, indicating that the N2 adsorptionedesorption
process in the composite is reversible from 0 torr to 1 torr. By
contrast, the no closed adsorptionedesorption isotherms of
the pure TiO2 reveal the irreversible N2 adsorptionedesorption process.
SEM images reveal that the composites contain uniformly
mixed fluffy clusters and curved layers (Fig. 3). The composites are fluffy and porous. The fluffy clusters nearly covered
the entire surface of the curved layers, and small clusters are
scattered in some areas. In Fig. 3b, a close observation

indicates that the clusters contain nanoparticles. The curved

layers and nanoparticles were graphene and TiO2 nanoparticles, respectively. Further TGA analysis of grapheneTiO2 in an air flow (the insert curve in Fig. 3b) displays a weight
loss of 30 wt. % from 50  C to 1000  C corresponding to the
oxidation of graphene in the sample, which indicated that the
content of TiO2 was about 70 wt. %.
In Fig. 4, TEM observations also show that nanocomposites
comprise graphene and TiO2 nanoparticles. The TiO2 nanoparticles clusters should be the product from the reaction of
TiCl4 and H2O. TiCl4 could be hydrolyzed into TiO2. The uniformity of nanocomposites prepared by vapor is good. The
TiO2 nanoparticles is evenly mixed with graphene, as shown
in the following large-scale TEM image (Fig. 4a). However, the
following amplification observations display that the TiO2
nanoparticles scattered on the surface of graphene often
clustered, some area of graphene surface was clean without
TiO2 nanoparticles, as shown in Fig. 4b and c.
At high magnification, obviously, some TiO2 nanoparticles
directly attached on the surface of graphene could be
observed, as shown in Fig. 4d, the direct contact between TiO2
and graphene could form an electrical conductivity network
between TiO2 and graphene, which will be useful for electron
transfer in the composite of graphene-TiO2. Given the existence of rich oxide-containing groups, such as hydroxyl, on
the GO surface, the hydroxy group could react with TiCl4 to
form a bond of TieO, which would be helpful in growing TiO2
on graphene [25,26]. The plane spacing of TiO2 was 0.35 nm

Fig. 3 e SEM images of graphene-TiO2 (a), TiO2 clusters loading on graphene and inserted TGA curve of graphene-TiO2 (b).

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Fig. 4 e Typical TEM images (aec) and HRTEM image (b) of graphene-TiO2 materials.

Fig. 5 e Chargeedischarge curve of graphene-TiO2 at 0.1 A/g (a). Specific discharge capacity of graphene-TiO2, TiO2 and
graphene at 0.1 A/g (b). Cyclic voltammetry test curve between 0.01 and 3.0 V at a scanning rate of 0.1 mV/s (c) and specific
discharge capacity at 0.05 A/g to 1 A/g (d) of graphene-TiO2.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 3 5 5 e3 6 0

(the insert picture in Fig. 4d), that was in accordance with the
spacing of the anatase TiO2 (101) crystal plane.
The graphene-TiO2 materials were used as a Na-ion battery
anode. In Fig. 5a and b, the initial discharge capacity of the
materials was 407.1 mAhg
1. In the second cycle, the
discharge capacity decreased to 240.0 mAh g
1, which is 58.9%
of the initial capacity. In subsequent cycles, the discharge
capacity of the graphene-TiO2 electrode continuously
decreased and delivered a capacity of 128.7 mAhg
1 at the
50th and 119.5 mAhg
1 at the 100th cycle. The rapid decrease
capacity in the initial cycles was speculated to be caused by
the formation of a solid electrolyte interface film caused by the
surface eOH groups of TiO2 prepared by hydrolytic reaction
and the carbon-based electrolyte and Na-ions irreversible
embedding into TiO2/graphene porous matrix [27]. After that,
the specific capacity becomes almost stable, which should be
related with the storage mechanism of stable Na intercalation reaction [17,27]. The nanocomposites showed a stable
discharge specific capacity 102 mAhg
1 after 390 cycles.
In comparison, the trend in the discharge capacity of the
TiO2 electrode with cycle is similar with that of grapheneTiO2. The initial discharge capacity is 336.8 mAhg
1, and the
second is 157.1 mAhg
1. From the 10th to the 100th cycle, a
relatively stable capacity about 60 mAhg
1 was obtained,
which is half that of graphene-TiO2. As for graphene, the
initial discharge capacity is 175.6 mAhg
1, the subsequent
cycle discharge capacity is only 2e10 mAhg
1 from the 10th to
the 100th cycle. So it could be concluded that graphene have
played an effective role to improve graphene-TiO2 electrochemical performance for Na-ion battery, but the contribution
to storage Na-ion could be neglected. In addition, the
morphology of cyclic voltammetry test curve is similar with
that of pure TiO2 in previous report (Fig. 5c) [23], which also
could be as a supporting evidence of the speculation that main
active materials is TiO2 for Na storage.
The chargeedischarge rate performance of the anode materials are one of important indicator for practical applications. Fig. 5d shows the rate test for graphene-TiO2 from
0.05 A/g to 1 A/g. At initial cycle test from the 1st to 15th at
0.1 A/g, the trend of discharge capacity reducing is the same as
the previous cycle stability test. With the increase of current
density, graphene-TiO2 electrode has shown a good test performance. At a high current density of 1.0 A/g from 26th cycle
to 45th cycle, the electrode discharge capacity could still be
kept at about 115 mAhg
1 (Fig. 5d). When the current density
was changed back to 0.1 A/g, the specific capacity of grapheneTiO2 increased to 145 mAhg
1. The ratio test shown that graphene-TiO2 could endure a large current and has a good ratio
capability for a high rate chargeedischarge energy storage
system.

Conclusions
A continuous and effective vapor reaction process was
developed to synthesize graphene-TiO2 materials. In the materials, the graphene was mono-dispersed in the composite
materials, which effectively improve the porosity and electrochemical properties of the materials. The specific area of
the composites is 28 m2/g, which is three times higher than

359

that of the reference TiO2. The composites are used as

lithium-ion battery anode materials. The stable discharge
specific capacity is 102 mAhg
1, which is 40% higher than that
of the reference pure TiO2.

Acknowledgments
This work is supported by The National Basic Research Program of China (Grant. No.: 51272176), the Key Projects of
Tianjin Municipal Natural Science Foundation of China
(13JCZDJC33900 and 14JCZDJC32200), National Basic Research
Program of China (973 Program, 2012CB933600), Academic
Innovation Funding of Tianjin Normal University (52XC1404),
the Youth Foundation of Tianjin Normal University (5RL128),
LPMT, CAEP (KF14006), and the National Natural Science
Foundation of China (51572194).

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