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3D anatase TiO2 hollow microspheres assembled with high-energy {001}
facets for lithium-ion batteries{
Yanlong Yu,a Xiaoliang Wang,b Hongyu Sun*c and Mashkoor Ahmad*d
Received 19th April 2012, Accepted 22nd June 2012
Published on 02 August 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20718D

DOI: 10.1039/c2ra20718d

3D anatase TiO2 hollow microspheres assembled with high-energy {001} facets have been synthesized
by a one-pot solution method and their lithium storage capacity are investigated. The structural and
compositional analysis of the mesoporous TiO2 product has been performed by X-ray diffraction
(XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy
(HRTEM) along with selected area electron diffraction (SAED). The Bruauer–Emmett–Teller (BET)
specific surface area has been calculated by the nitrogen isotherm curve and pore size distribution of
TiO2 microspheres has been determined by the Barret–Joyner–Halenda (BJH) method. It has been
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found that the as-prepared TiO2 electrodes delivered high capacity, good cycling stability and rate
capability. The improved electrochemical performance is attributed to the hollow nature and exposed
high-energy {001} facets of the 3D assembled structure. Therefore, such a structure can be considered
to be an attractive candidate as an electrode material for LIBs.

1. Introduction
Rechargeable lithium-ion batteries (LIBs) are one of the most
important energy storage devices for portable electronics and
electric vehicles due to their advantages of high energy density,
long cycling life and environmental benignity.1–3 It is widely
accepted that the overall performance of LIBs is highly
dependent on the inherent properties of the electrode materials.4
For nanostructured electrode materials, hollow interiors gen-
erally leads to improved energy density, better capacity retention
and superior rate capability, which are due to the large surface
area, numerous active sites, short mass and charge diffusion
distance, and efficient accommodation of volume changes during
the charging and discharging process.5
Anatase titania (TiO2) is of great importance for both
fundamental studies and technological applications in the field
of energy storage.6–9 Although anatase TiO2 delivers a lower
capacity (y170 mA h g21 vs. y372 mA h g21 for commercial
LIB anodes, graphite) at a higher potential of about 1.7 V vs.
Li+/Li, the ease of structural tailoring, the low volume expansion
upon cycling, good stability and absence of lithium plating,
endow it with great potential to be charged/discharged at high
a overlap with each other to reduce the overall surface energy.
A Department of Petrochemical, Northeast Petroleum University at
Qinhuangdao, Qinhuangdao, 066004, P. R. China
b
State Key Laboratory of Metastable Materials Science and Technology,
Yanshan University, Qinhuangdao, 066004, P. R. China
c
Department of Material Science and Engineering, Tsinghua University,
Beijing, 100084, China. E-mail: hysun.2008@yahoo.com.cn
d
Nanomaterials Research Group, Physics Division PINSTECH, P. O.
Nilore, Islamabad, 44000, Pakistan.
E-mail: mashkoorahmad2003@yahoo.com
{ Electronic supplementary information (ESI) available. See DOI:
10.1039/c2ra20718d
current rates for extended cycling, which can hardly be achieved
by other types of anodes.9 The size, shape and assembly of
various anatase TiO2 nanostructures have been intensively
investigated to optimize the Li-ion storage properties.10–19 It
was found that Li-ion insertion was favored on the {001} surface
of anatase TiO2, which has a more open structure and short path
for lithium ion diffusion along this direction.16–20 It is thus
believed that the synthesis of anatase TiO2 exposed with {001}
facets is beneficial for improvement the performance of LIBs.
Theoretical calculations21 show that the surface energies of {001}
and {101} facets of anatase TiO2 are 0.90 and 0.44 J m22,
respectively. Therefore, anatase TiO2 crystals are dominantly
bound by thermodynamically stable and less chemically reactive
{101} facets. Thus, growth of nano/microanatase TiO2 crystals
with exposed high-energy {001} facets is highly challenging. An
important breakthrough in preparation of anatase TiO2 single
crystals with exposed {001} facets was achieved by Yang et al.22
Following their work, numerous studies have been reported on
the synthesis of TiO2 crystals with exposed {001} facets for
photocatalytic and lithium-ion batteries applications.23–26
However, most of these anatase TiO2 are crystals with two-
dimensional sheetlike structures, which make the sheets easily
Preventing the aggregation of these crystals with large amount of
exposed {001} facets is a big challenge. One promising way to
obtain stable TiO2 sheets is to assemble them into a self-ordered
three-dimensional (3D) architecture.27
In this work, we describe a one-pot synthesis of 3D anatase
TiO2 hollow microspheres with exposed high-energy {001}
facets. The excellent lithium-storage properties of the as-
prepared TiO2 products have been demonstrated.

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2. Experimental section
2.1 Materials synthesis
All the chemicals are of analytical grade and used as received
without further purification. Deionized water was used through-
out and Ti powder was used as titanium source. In a typical
synthesis, 20 mg of Ti powder was dispersed into a solution
containing 27 ml of H2O, 3 ml of H2O2 (30%, A.R.) and 0.1 ml of
hydrofluoric acid (40 wt%) by ultrasonicaiton for 10 min giving a
transparent yellow solution. The reaction solution was then
transferred to a 50 mL Teflon-lined stainless steel autoclave and
kept in an electric oven at 180 uC for 12 h. The autoclave was
Published on 02 August 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20718D
then taken out from the oven and left to cool down to room
temperature. The white precipitate obtained was washed
thoroughly with distilled water and ethanol three times and
then dried at 80 uC for 12 h.
2.2 Materials characterization
The product morphology and crystal structure was examined
using field-emission scanning electron microscopy (FESEM;
Hitachi, S4800, 5 kV), transmission electron microscopy (TEM;
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JEOL, JEM-2011, 200 kV; FEI, Tecnai G20, 200 kV) and high-
resolution TEM (HRTEM, FEI, Titan 80–300, 300 kV).
Crystallographic information for the samples was collected using
a Bruker Model D8 Advance X-ray powder diffractometer
(XRD) Cu-Ka irradiation (l = 1.5418 Å). The Barret–Joyner–
Halender (BET) surface area of the powders was analyzed by
nitrogen adsorption–desorption isotherm measurement at 77 K
in a Micromeritics ASAP 2010 system. The sample was degassed
at 180 uC before nitrogen adsorption measurements. The BET
surface area was determined by a multipoint BET method. A
desorption isotherm was used to determine the pore size
distribution via the Barret–Joyner–Halender (BJH) method,
assuming a cylindrical pore model. The nitrogen adsorption
volume at the relative pressure (P/P0) of 0.994 was used to
determine the pore volume and average pore size.
2.3 Assembly of electrochemical cells
To measure the electrochemical performance, composite electro-
des were constructed by mixing the active materials, conductive
carbon black and polyvinylidene fluoride (PVDF), in a weight
ratio of 70 : 20 : 10. The mixture was prepared as a slurry in
N-methylpyrrolidinone and spread onto copper foil by using the
doctor-blade technique. The electrode was dried under vacuum
at 120 uC for 5 h to remove the solvent before pressing. Then the
electrodes were cut into disks (12 mm in diameter) and dried at
100 uC for 24 h in vacuum. The cells were assembled inside an
Ar-filled glove box by using a lithium-metal foil as the counter
electrode and the reference electrode and microporous poly-
propylene as the separator. The electrolyte used was 1 M LiPF6
in ethylene carbonate (EC)–dimethyl carbonate (DMC) solvent
(1 : 1 w/w). Assembled cells were allowed to soak overnight, and
then electrochemical tests on a LAND battery testing unit were
performed. Galvanostatic charge and discharge of the assembled
cells were performed at different current rates (1 C = 170 mA g21)
between voltage limits of 1 and 3 V (vs. Li) at room temperature.
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3. Results and discussion
3.1 Structure, morphology and BET surface area
The crystal structure of the resulting product was confirmed by
XRD as shown in Fig. 1a. All of the identified peaks can be
perfectly indexed to anatase TiO2 (JCPDS No. 21-1272), and no
peaks of impurities are observed, indicating the phase-pure
nature of the product. Moreover, the relatively high peak
intensities imply that the products are highly crystalline. The
relative ratio of the (004) peak intensity to that of the (101) peak
of anatase TiO2 is ca. 30%, which is larger than that of the
standard pattern (20%), implying the oriented growth of the
sample along the (001) direction. This is further confirmed by
HRTEM characterization as discussed later.
Fig. 1b shows the low-magnification FESEM image of the
product which consists of hollow TiO2 microspheres uniformly
distributed on the substrate. The average diameter of the
microsphere is y1 mm. The high-magnification image of the
particles is shown in the inset of Fig. 1b, and it is interesting to
find that the surfaces of these microspheres are covered by many
square-shaped crystalline facets. The FESEM image of broken
microspheres reveals the hollow nature of these microspheres
(indicated by white arrows in Fig. 1c). The contrast between
the edge and center further confirms the hollow interior.
Furthermore, it can be seen that the interior of the hollow
spheres is not as flat as the exposed exterior surface, thus, it can
be determined that the interior surface is not constituted by high-
energy {001} facets. Nitrogen adsorption–desorption isotherms
were measured to determine the specific surface areas and pore
size distribution of the TiO2 hollow microspheres with exposed
{001} facets (Fig. 1d). The BET specific surface area of the
product is ca. 43.3 m2 g21 which is slightly smaller than that of
P25 (55.1 m2 g21).28 The isotherm corresponding to the product
is of type IV with two capillary condensation steps, implying
bimodal pore size distributions in the mesoporous and macro-
porous regions.29 The pore size distributions are calculated from
the desorption branch of the nitrogen isotherm by the BJH
method. The bimodal mesopore size distribution is further
confirmed by the corresponding pore size distributions (inset in
Fig. 1d).
Two typical TEM images of a single TiO2 microsphere are
displayed in Fig. 2a and b. The contrast between the dark edge
and pale center further confirms the hollow interior and
surrounding crystalline shell, which is in good agreement with
the FESEM observations and BET surface analysis. More
detailed structural information of the TiO2 microsphere is
obtained by aberration-corrected TEM, which was operated at
300 kV with spherical aberration close to zero with near
Gaussian focus being used. The HRTEM image of an individual
TiO2 plate from the microsphere shows perpendicular lattice
spacing of 0.192 nm representing the (200) and (020) atomic
planes of the anatase TiO2 (Fig. 2c). The corresponding fast-
Fourier transform (FFT) pattern (inset in Fig. 2c) confirms the
single-crystal nature of a square-shaped crystallite with the zone
axis being [001]. A corresponding FFT-filtered TEM image of
the tetragonal atomic arrangement on the (001) surface is shown
in Fig. 2d, which is similar with Yang’s report.22 The line profile
through the direction shown in Fig. 2d further demonstrates the
exposed surfaces are high-energy {001} facets (Fig. 2e). The
This journal is ß The Royal Society of Chemistry 2012

Published on 02 August 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20718D
Fig. 1 (a) XRD pattern and (b and inset) FESEM images of as-synthesized 3D anatase TiO2 microspheres. (c) High-magnification FESEM image of
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broken microspheres, demonstrating the hollow nature. (d and inset) Nitrogen adsorption–desorption isotherms and corresponding pore size
distribution curves of the sample.
above results reveal that 3D anatase TiO2 hollow microspheres
assembled with high-energy {001} facets have been successfully
synthesized by a facile one-pot method, which is anticipated to
show good lithium-storage properties.
Fig. 2 (a, b) TEM images and (c) HRTEM image of TiO2 microspheres
(inset: corresponding FFT pattern). (d) FFT-filtered TEM image
recorded from the area indicated by white box in (c). (e) Intensity plot
of profile along the direction indicated by the yellow arrow in (d).
This journal is ß The Royal Society of Chemistry 2012
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3.2 Formation of TiO2 hollow microspheres
The formation process and formation mechanism of the TiO2
hollow microspheres have been investigated in our recent work.30
The formation mechanism of the hollow TiO2 structures was
investigated by time-dependent evolution experiments.
Briefly, HF reacts with metallic Ti at the first stage, leading to
the formation of titanium fluoride complexes, then the Ti4+
reacts with H2O2 to form yellow peroxotitanium acid,
Ti2O5(OH)x(x22)2 (x = 1–6). Under solvothermal conditions,
the water in the reaction promoted the hydrolysis of perox-
otitanium acid to form anatase TiO2 particles. These particles
quickly aggregated to form solid spheres because of their high
surface energy. With time hollow spheres were formed via
Ostwald ripening. During the transformation to the hollow
spheres, the inner part of the solid spheres gradually dissolved
and was recrystallized on the shell of the spheres to finally form
hollow spheres. Meanwhile, the surface fluorination via dis-
sociative adsorption of HF makes the [001] direction a
preferential crystal growth direction due to the reduced {001}
facet surface energy. This leads to the formation of TiO2
microspheres having protrusive square-shaped surface structures
with exposed plane {001} facets. Finally, the oriented plates
further increased in thickness by consuming the central part of
the spheres.
3.3 Electrochemical measurements
The electrochemical properties of the as prepared sample as the
anode material for lithium-ion batteries are investigated. Fig. 3a
shows the charge–discharge voltage profiles for the first three
cycles at a current rate of 1C (170 mA h g21). Two dominant
voltage plateaus appear at y1.65 and y2.10 V during the
discharge and charge processes, which correspond to the lithium
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Published on 02 August 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20718D
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Fig. 3 (a) Charge/discharge curves of the first three cycles of the TiO2
electrodes at a charge/discharge rate of 1 C. (b) The cycling performance
and corresponding Coulombic efficiency of the TiO2 electrodes at a
charge/discharge rate of 1 C and cycling performance of reported anatase
TiO2 nanoparticles at a rate of 0.1 C for comparison.27
insertion and deinsertion, respectively. This is in good agreement
with previous reports.16–18,31 The first discharge capacity is
235 mA h g21 and the charge capacity is 208 mA h g21, yielding
an irreversible capacity loss of 11.5%. Such a low initial
irreversible capacity loss might be attributed to the exposed
high-energy {001} facets. The subsequent Coulombic efficiency
(the ratio of charge capacity to discharge capacity) quickly
increases to 96.2% and 99% in the second and third cycles,
respectively, which is mainly due to that the trapping of Li+ ions
inside the TiO2 structure decreases rapidly upon the following
cycles.9 Fig. 3b shows the charge/discharge capacity and
Coulombic efficiency vs. cycle numbers between 1 and 3 V at a
constant current density of 1C. It can be seen that the as-
prepared material shows good cyclic capacity retention during
cycling. A reversible capacity of 157 mA h g21 can be retained
after 50 cycles with about 75% retention as compared with the
first reversible capacity. The Coulombic efficiency reached 99%
at the second cycle and remained steady thereafter. The charge–
discharge capacity of the TiO2 hollow microspheres electrode
was also compared with reported anatase TiO2 nanoparticles
(25 nm in diameter),23 as shown in Fig. 3b. The experimental
conditions for TiO2 NPs are similar to our case except that they
were cycled with a low current rate of 0.1 C. It can be seen that
the first discharge capacity of the anatase nanoparticles reaches
151 mA h g21 but further cycling leads to a drastic capacity
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Fig. 4 (a) Cycling performance of the TiO2 electrodes at various current
rates. (b) HRTEM image of the TiO2 electrodes after rate capability
testing (50 cycles). The top and bottom insets in (b) show the
corresponding FFT pattern and TEM image, respectively.
decay to 57 mA h g21 after 50 cycles. The compared results
further confirm the superior lithium storage performance of our
sample. The rate capability is an important parameter for the
applications of LIBs in the fields of electric vehicles and portable
power tools. Fig. 4a shows the cycling performance of the
anatase TiO2 hollow microspheres electrode at various current
rates. It can be found that after the first 10 cycles at the rate of
1 C, the discharge capacity reaches about 156 mA h g21, and
then it slightly reduces to 135 and 130 mA h g21 at rates of 2 and
5 C, respectively. Even for a rate as high as 10 C, the electrode
can deliver a reversible capacity of 90 mA h g21. More
interestingly, when the current rate is returned to the initial
value of 1 C, the electrode resumes its original capacity of about
150 mA h g21 after 10 cycles, indicating that the anatase TiO2
hollow microspheres assembled with high-energy {001} facets
possess good cycling stability. The performance of LIBs is similar
with the reported values by Lou et al. under the same testing
conditions.16 The bottom inset in Fig. 4b shows the TEM image of
the anatase TiO2 hollow microspheres electrode after rate capability
testing (50 cycles). The cycled sample still maintains the morphology
with 3D hollow microspheres, which is constituted by square-shaped
crystalline facets. It can be seen that the sample still maintains the
initial intact spherical morphology after cycling testing except for a
small fraction of incomplete hollow spheres (Fig. S1, ESI{).
HRTEM and corresponding FFT patterns demonstrate that the
This journal is ß The Royal Society of Chemistry 2012

exposed square-shaped facets are high-energy {001} surfaces of
anatase TiO2 (Fig. 4b and top inset). The results reveal the good
structural and morphological stabilities of anatase TiO2 hollow
microspheres during charge/discharge cycling.
The high capacity and good rate capability and cycling
stability can be attributed to the following reasons. (1) The
hollow nature of the product. Firstly, the interior of TiO2 hollow
microspheres can provide extra active sites for the storage of
lithium ions, which is beneficial for enhancing the specific
capacity. Secondly, the hollow structures can accommodate the
local volume change upon charge/discharge cycling and is able to
alleviate the problem of pulverization and aggregation of the
Published on 02 August 2012 on http://pubs.rsc.org | doi:10.1039/C2RA20718D
electrode material, hence improving the cycling performance.
Moreover, the hollow structure can reduce the effective diffusion
distance for lithium ions and electrons, resulting in good rate
capabilities. (2) Exposed high-energy {001} facets. Anatase TiO2
crystals with exposed {001} facets exhibit an enhanced Li-ion
insertion/extraction kinetics, including better reversibility and
excellent rate capabilities. (3) 3D assembled structure. The 3D
hierarchical architecture assembled with high-energy facets is
favored for preventing the aggregation of these nano/micro-
crystals, which is of importance for the cycling stability.
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4. Conclusions
In conclusion, 3D anatase TiO2 hollow microspheres assembled
with high-energy {001} facets were successfully synthesized by a
one-pot solution method. When used as the anode materials of
Li-ion batteries, the as-prepared TiO2 sample delivered high
capacity, good cycling stability and rate capability. It is believed
that the excellent electrochemical performance can be attributed
to the hollow nature and exposed high-energy {001} facets of the
3D assembled electrode structure.
Acknowledgements
This work is financially supported by China Postdoctoral
Science Foundation (20110490024).
References
1 F. Y. Cheng, J. Liang, Z. L. Tao and J. Chen, Adv. Mater., 2011, 23, 1695.
2 C. Liu, F. Li, L. P. Ma and H. M. Cheng, Adv. Mater., 2010, 22, E28.
This journal is ß The Royal Society of Chemistry 2012
View Online
3 M. Winter and R. J. Brodd, Chem. Rev., 2004, 104, 4245.
4 M. K. Song, S. Park, F. M. Alamgir, J. Cho and M. L. Liu, Mater.
Sci. Eng., R, 2011, 72, 203.
5 Z. Y. Wang, L. Zhou and X. W. Lou, Adv. Mater., 2012, 24, 1903.
6 M. Wagemaker, A. P. M. Kentgens and F. M. Mulder, Nature, 2002,
418, 397.
7 A. V. Subramanian, A. Karki, K. I. Gnanasekar, F. P. Eddy and B.
Rambabu, J. Power Sources, 2006, 159, 186.
8 X. W. Lou and L. A. Archer, Adv. Mater., 2008, 20, 1853.
9 H. B. Wu, J. S. Chen, H. H. Hng and X. W. Lou, Nanoscale, 2012, 4,
2526.
10 H. B. Wu, J. S. Chen, X. W. Lou and H. H. Hng, Nanoscale, 2011, 3,
4082.
11 J. Wang, Y. K. Zhou, Y. Y. Hu, R. Hayre and Z. P. Shao, J. Phys.
Chem. C, 2011, 115, 2529.
12 J. F. Ye, W. Liu, J. G. Cai, S. Chen, X. W. Zhao, H. H. Zhou and
L. M. Qi, J. Am. Chem. Soc., 2011, 133, 933.
13 Y. Wang, X. W. Su and S. Lu, J. Mater. Chem., 2012, 22, 1969.
14 Z. X. Yang, G. D. Du, Q. Meng, Z. P. Guo, X. B. Yu, Z. X. Chen,
T. L. Guo and R. Zeng, J. Mater. Chem., 2012, 22, 5848.
15 S. Myung, N. Takahashi, S. Komaba, C. S. Yoon, Y. Sun, K. Amine
and H. Yashiro, Adv. Funct. Mater., 2011, 21, 3231–3241.
16 S. J. Ding, J. S. Chen, Z. Y. Wang, Y. L. Cheah, S. Madhavi, X. Hu
and X. W. Lou, J. Mater. Chem., 2011, 21, 1677.
17 J. S. Chen, Y. L. Tan, C. M. Li, Y. L. Cheah, D. Luan, S. Madhavi,
F. Y. C. Boey, L. A. Archer and X. W. Lou, J. Am. Chem. Soc., 2010,
132, 6124.
18 J. H. Liu, J. S. Chen, X. F. Wei, X. W. Lou and X. W. Liu, Adv.
Mater., 2011, 23, 998.
19 C. H. Sun, X. H. Yang, J. S. Chen, Z. Li, X. W. Lou, C. Z. Li, S. C.
Smith, G. Q. Lu and H. G. Yang, Chem. Commun., 2010, 46, 6129.
20 S. W. Liu, J. G. Yu and M. Jaroniec, Chem. Mater., 2011, 23, 4085.
21 U. Diebold, Surf. Sci. Rep., 2003, 48, 53–229.
22 H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M.
Cheng and G. Q. Lu, Nature, 2008, 453, 638.
23 S. W. Liu, J. G. Yu and M. Jaroniec, J. Am. Chem. Soc., 2010, 132,
11914.
24 Q. J. Xiang, J. G. Yu and M. Jaroniec, Chem. Commun., 2011, 47,
4532–4534.
25 K. L. Lv, B. Cheng, J. G. Yu and G. Liu, Phys. Chem. Chem. Phys.,
2012, 14, 5349.
26 Q. J. Xiang and J. G. Yu, Chin. J. Catal., 2011, 32, 525–531.
27 Z. Q. Sun, J. H. Kim, Y. Zhao, F. Bijarbooneh, V. Malgras, Y. Lee,
Y. Kang and S. X. Dou, J. Am. Chem. Soc., 2011, 133, 19314.
28 J. G. Yu, Q. J. Xiang, J. R. Ran and S. Mann, CrystEngComm, 2010,
12, 872.
29 K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A.
Pierotti, J. Rouquerol and T. Siemieniewska, Pure Appl. Chem., 1985,
57, 603.
30 X. Wang, H. He, Y. Chen, J. Zhao and X. Zhang, Appl. Surf. Sci.,
2012, 258, 5863.
31 H. Ogihara, M. Sadakane, Y. Nodasaka and W. Ueda, Chem.
Mater., 2006, 18, 4981.
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