Electrochimica Acta 210 (2016) 206–214

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

Porous TiO2 urchins for high performance Li-ion battery electrode:

facile synthesis, characterization and structural evolution
Yi Caia , Hong-En Wanga,* , Shao-Zhuan Huanga , Muk Fung Yuenb , Heng-Hui Caia ,
Chao Wanga , Yong Yua , Yu Lia , Wen-Jun Zhangb,**, Bao-Lian Sua,c,***
a
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 122 Luoshi Road, 430070, Wuhan,
Hubei, China
b
Department of Physics and Materials Science and Center Of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong, China
c
Laboratory of Inorganic Materials Chemistry (CMI), University of Namur, 61 rue de Bruxelles, B-5500 Namur, Belgium

A R T I C L E I N F O A B S T R A C T

Article history:
Received 30 March 2016 Porous TiO2 urchins have been synthesized by a hydrothermal route using TiO2/oleylamine as precursors
Received in revised form 17 May 2016 with subsequent ion-exchange and calcination. The resultant material consists of porous spherical cores
Accepted 20 May 2016 and nanochains-constructed shells with straight channels. Electrochemical measurements indicate the
Available online 21 May 2016 TiO2 urchins deliver superior lithium storage capability in terms of high capacity (206.2 mA h g
1 at 0.5 C),
superior rate performance (94.4 mA h g
1 at 20 C) and stable cycling stability (94.3% capacity retention
Keywords: over 1000 cycles at 10 C versus the third cycle). Such performance enhancement is mainly due to the
TiO2 increased electrode/electrolyte contact interface, reduced Li+ diffusion pathways and improved mass
porous structure
transfer of electrolyte in the unique 3D interconnected hierarchical network. In addition, ex-situ XRD,
anode materials
SEM and TEM analyses further reveal high structure integrity of the porous TiO2 urchins during the
Li ion battery
electrochemistry electrochemical lithiation, leading to enhanced lithium storage stability. Moreover, we detected that
some anatase nanocrystals evolved into electrochemically inactive Li1TiO2 dots (10 nm in size) during
long-term electrochemical cycling. Our findings provide more insights for better understanding of the
structure evolution and capacity decay mechanism in porous TiO2 nanostructures.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction small volume changes upon Li+ uptake/removal, and absence of

Lithium ion batteries (LIBs) have played a crucial role in
powering portable electronic devices in the past two decades [1].
They are now being further improved for emerging energy-storage
applications in (hybrid, plug-in) electric vehicles, smart grids and
intermittent renewable energies from solar and wind. Despite their
commercial success, improvements in power, cost, durability and
safety are still highly desired [2]. Among various electrode
materials, TiO2 has attracted considerable interest as alternative
anode because of its high abundance, nontoxicity, high activity,
* Corresponding author. Tel.: +86 27 87855322; fax: +86 27 87879468.
** Corresponding author. Tel.: +852 34427433; fax: +852 34420538.
*** Corresponding author at: Laboratory of Inorganic Materials Chemistry (CMI),
University of Namur, 61 rue de Bruxelles, B-5500 Namur, Belgium.
Tel.: +32 81 724531; fax: +32 81 725414.
E-mail addresses: hongenwang@whut.edu.cn, hongen.wang@gmail.com
(H.-E. Wang), apwjzh@cityu.edu.hk (W.-J. Zhang), bao-lian.su@unamur.be
(B.-L. Su).
solid-electrolyte interphase layer for better operation safety [3–5].
The electrochemical performance of TiO2 strongly relies on its
polymorphs [6,7], crystallinity [8], grain size [9], morphology
[10,11], porosity and composition [12,13], which can determine the
Li+ diffusion and electron transport. In particular, much work has
been devoted to the controllable synthesis and electrochemical
characterization of various TiO2 nanostructures with tunable
morphologies [14–16] and compositions [17,18], either in pure
phases or mixed polymorphs [19–25], as well as nanocomposites
hybridized with carbon nanotubes [26], and reduced graphene
oxides [6,27–29]. Among these, urchin-like TiO2 has gained much
attention due to its unique structure and electrochemical
performance [30–32]. For example, Park et al. synthesized
urchin-like rutile TiO2 submicron spheres composed of single-
crystalline nanorods. After coating with amorphous carbon layer, it
could deliver a reversible capacity of 165.7 mA h g
1 after 100
cycles at 0.2 C [33]. Meanwhile, porous or hollow TiO2 nano-
structures [34–43] can offer more active sites for Li+ storage due to
their high surface area, good accommodation of volume change
during (de)lithiation and shortened pathways for fast Li+ and

http://dx.doi.org/10.1016/j.electacta.2016.05.140
0013-4686/ã 2016 Elsevier Ltd. All rights reserved.
 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214 207

electron transport, leading to enhanced electrochemical perfor- 2. Experimental

mance. Porous TiO2 nanostructures with well-defined morphol-
ogies and pore structures can be prepared by template-directing
approaches. For example, TiO2 nanocages with uniform shells and
tunable sizes have been fabricated by using Cu2O polyhedra as
sacrifice templates [44]; however, conventional template-based
synthetic routes may require the removal of hard- or soft-
templates in the following steps, leading to increased synthetic
costs and environmental concerns.
In addition, recent study discloses mesoporous TiO2 material
can undergo evident structure degradation and capacity loss upon
electrochemical cycling in opposition to what is expected for a long
time [45]. The structure change has been primarily ascribed to
irreversible lattice swelling/shrinkage caused by Li+ concentration
gradient in porous framework during initial (de)lithiation.
Therefore, design of rational pore structure and deeper under-
standing of structure evolution of porous TiO2 electrode during
cycling are very important and highly desired.
In this work, we report the designed synthesis of porous TiO2
urchins constructed from nanochains using TiO2/oleylamine
composite as precursor via an in-situ self-sacrificing template
method. The resultant TiO2 material exhibits superior electro-
chemical performance as anode for LIBs. Post-mortem character-
izations validate high structure stability of the TiO2 material during
cycling. More importantly, we observe the evolution of trace 10-
nm Li1TiO2 crystalline dots that are randomly distributed within
the TiO2 host after long-term cycling. Our findings can provide
more insights into the deeper understanding of the high Li+ storage
capability of porous TiO2 nanostructures as well as their capacity
decay mechanism upon cycling.
2.1. Materials synthesis
All the chemicals were analytically pure grade and used as
received without further purification.
Amorphous TiO2/oleylamine spheres were synthesized refer-
ring to literature work [46] with little modification (oleylamine
was used as surfactant) and served as precursor for following
experiments.
Titanate urchins were prepared by hydrothermal reaction of
TiO2/oleylamine precursor in an alkaline solution. In a typical
procedure, 0.2 g of precursor was dispersed in 40 mL of H2O and
20 mL of ethanol containing 12 g of NaOH. Then, the suspension
was transferred into an autoclave (with a PTFE liner, 100 mL
capacity) and heated at 160  C for 12 h. The resultant white
precipitates were rinsed with ethanol and distilled water, and
dried at 80  C in air for 12 h. Protonated titanate (H-titanate)
sample was obtained by soaking the titanate sample in 0.12 M of
HCl solution for 2 h to exchange the interlayer Na+ with H+ and then
thoroughly rinsed with deionized water and dried at 80  C for 12 h
in air.
Porous TiO2 urchins were obtained after thermal treatment of
the H-titanate sample at 450  C for 2 h in air with a heating rate of
2  C min
1.
2.2. Material characterizations
Crystal structures of the samples were analyzed by powder X-
ray diffraction (XRD) patterns recorded on a Bruker Diffractometer
operated at 40 kV and 40 mA with Cu Ka radiation. Rietveld

Fig. 1. Schematic illustration of the fabrication process of the porous TiO2 urchins. (a) TiO2/oleylamine composites, (b) out-diffusion of oleylamine from precursor and partial
conversion of TiO2 nuclei into titanate fragments during hydrothermal process, (c) titanate nanosheets-assembled flowers, (d) titanate nanotubes-constructed urchins, (e)
porous TiO2 urchins, (f) magnified portion of a TiO2 nanochain constructed from connected nanocrystals.
208 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214
refinement of XRD pattern has been performed using Maud
program [47]. Morphologies and element composition data of the
samples were obtained by a Hitachi S4800 scanning electron
microscope (SEM) equipped with an energy dispersive X-ray (EDX)
analyzer. Transmission electron microscopy (TEM) and high
resolution transmission electron microscopy (HRTEM) images
were acquired on a JEOL JEM-2100F electron microscope operated
at an acceleration voltage of 200 kV. Fourier transform infrared
spectroscopy (FT-IR) was performed with a Bruker Vertex 80 V FT-
IR spectrometer. Nitrogen sorption experiments were performed
using a Micrometrics, TriStar II 3020 system operated at 77 K. Prior
to the adsorption experiments, the samples were degassed at
200  C for 12 h.
2.3. Electrochemical Measurements
Electrochemical properties of the as-synthesized porous TiO2
urchins and reference Degussa P25 nanoparticles were measured
using CR2025 Li-half cells. The working electrode was prepared by
evenly spreading a slurry of 70 wt% TiO2, 20 wt% acetylene black
and 10 wt% polyvinylidenedifluoride binder onto a Cu current
collector. In both cases, a Li metal foil was used as the counter
electrode and reference electrode. 1 M LiPF6 dissolved in ethylene
carbonate/dimethyl carbonate (1:1 w/w) was used as the working
electrolyte, and Celgard 2400 polypropylene film served as the
separator. The coin cells were assembled in a glove-box filled with
ultrapure Ar gas with oxygen and water contents below 1 ppm. The
mass loading of the active material is about 11.5 mg. Galvano-
static discharge/charge experiments were performed on a
multichannel battery testing system (LAND CT2001A) over a
potential range of 31 V vs. Li/Li+. Cyclic Voltammetry (CV)
measurements were recorded on a CHI 604E electrochemical
workstation at varying scan rates from 0.1 to 1 mV s
1 within a
potential window of 31 V (vs. Li/Li+). Electrochemical impedance
spectra (EIS) were recorded on an electrochemical workstation
(Autolab PGSTAT302N) in the frequency range from 100 kHz to
Fig. 2. Microstructure characterizations of the titanate samples obtained by hydrothermal reaction for different time. (a) XRD patterns of the titanate samples prepared for 1 h
(1), 12 h (2), and H-titanate sample via ion-exchange (3); (b–d) SEM images of titanate samples prepared for 0.5 h, 1 h, and 12 h, respectively; (e) TEM image of the titanate
sample prepared for 12 h; (f) SEM image of the H-titanate sample after ion-exchange.
0.01 Hz at an amplitude of 10 mV. All the electrochemical tests
were performed at room temperature.
3. Results and discussion
Fig. 1 schematically illustrates the fabrication process of the
porous TiO2 urchins using TiO2/oleylamine composite as precursor.
The composite precursor is prepared by a modified sol-gel route
[46] and consists of amorphous spheres with a mean size of
500 nm (Fig. S1). According to the previous report, the TiO2 nuclei
and oleylamine molecules hybridize together uniformly by
hydrogen-bonding interaction between TiO2 and
NH2 groups
(Fig. 1a and S2a) [46].
Next, the composite precursor can be converted into titanate
intermediates by hydrothermal reaction (Fig. 1b–d). Hydrothermal
treatment accelerates the out-diffusion and dissolution of oleyl-
amine molecules in the ethanol, leading to the weakening of
hydrogen-bonding attraction between TiO2 and oleylamine (Fig. 1b
and S2b). Meantime, the strong interaction between exposed TiO2
colloids and hydroxyl ions (OH
) disrupts some specific Ti-O-Ti
bonds and generates new Ti-O-H bonds [48], leading to the
formation of titanate fragments (Fig. 1b). XRD patterns show the
titanate crystallites can be formed after a short reaction time. As
shown in Fig. 2a-1, the titanate product obtained after 1 h has a
body-centered orthorhombic Na2Ti2O5H2O structure consisting of
2D edge-shared [TiO6] octahedra sheets [49]. The titanate product
obtained after 12 h retains the same phase structure with an
enhanced crystallinity, characterized by the sharper diffraction
peaks (Fig. 2a-2). In addition, the diffraction peak of (200) plane
shifts slightly to a higher degree due to the contraction of interlayer
spacing. SEM characterization reveals the titanate samples
undergo a series of morphology evolution during the hydrothermal
process. As shown in Fig. 2b, the sample prepared after 0.5 h is
characterized by spherical particles consisting of thin laminar
sheets with a thickness of 3 nm and 30 nm lateral sizes. After
reaction for 1 h, the titanate sample is composed of nanotubes with
 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214
Fig. 3. (a) XRD pattern, (b) SEM image, (c) TEM and (d) HRTEM micrographs of the as-obtained TiO2 material. The insets on the top right and bottom right in (d) are the FFT
patterns of an anatase grain and TiO2-B grain labeled by the large and small dashed squares, respectively.
diameters of 12 nm and lengths of 100 nm (Fig. 2c). The shape
evolution from laminar sheets to hollow tubes adheres to the “self-
curling” mechanism driven by reducing total system energy via
surface energy minimization and elimination of crystal defects
[48]. After 12 h of reaction, the resultant porous titanate urchins
are constructed by longer nanotubes with 8 nm diameters,
2 nm wall thickness and lengths up to 2 mm (Fig. 2d, e). The
similar tube diameters of the two samples prepared after 1 h and
12 h hint the titanate nanotubes preferentially grow larger by
oriented-attachment of adjacent shorter ones between two tip
ends. Moreover, the EDX pattern (Fig. S3) further confirms the
existence of Na, Ti, O elements in the titanate sample.
We note that the ethanol/water solvent and TiO2/oleylamine
composite precursor play an important role in the formation of
such unique titanate nanostructures. Without ethanol, tiny
titanate nanosheets-assembled flowers are obtained in our
hydrothermal experiments (Fig. S4a). This result is possibly
ascribed to the adsorption of oleylamine on the surfaces of the
laminar titanate sheets, which prevents their further curling into
nanotubes due to a steric hindrance effect [50]. In contrast, the
ethanol in the solvent can dynamically dissolve the oleylamine
molecules during hydrothermal process, facilitating the structure
evolution of titanate fragments. In addition, random titanate 1D
nanostructures with irregular particle sizes are formed if
commercial P25 nanoparticles are used as the starting precursor
(Fig. S4b). It is speculated that the oleylamine in the precursor can
slow down the reaction rate between TiO2 and OH
, featuring the
formation of uniform hierarchical nanostructures. Nonetheless,
our synthetic strategy herein provides a general approach for the
facile fabrication of an array of urchin-like titanate and TiO2
nanostructures with tunable configurations and polymorphs by
further optimizing experimental parameters.
209
The titanates can be readily converted into porous TiO2 urchins
via ion-exchange and annealing. After ion-exchange, the resultant
protonated titanate (H-titanate) sample has an orthorhombic
H2Ti2O5H2O phase (JCPDS Card No. 47-0124) with similar peak
positions to its parent titanate (Fig. 2a-3) [49]. The intensity change
of (200), (110) and (310) diffraction peaks is mainly due to the
displacement of Na+ by H+ [49]. SEM image (Fig. 2f) reveals the
obtained H-titanate sample retains an urchin-like morphology.
TEM and high-magnification TEM micrographs (Fig. S5) further
confirm the as-obtained H2Ti2O5H2O product consists of urchin-
like porous spheres constructed by interlinked nanotubes with
diameters of ca. 8 nm. The EDX spectrum (Fig. S6) further evidences
the Na+ ions have been virtually replaced by H+ ions. After
annealing, the resultant TiO2 sample (Fig. 3a) has a tetragonal
anatase structure with a space group of I41/amd (JCPDS Card No.
21-1272) [51]. The sharp diffraction peaks indicate the high
crystallinity of the TiO2 product. Rietveld refinement of the XRD
pattern was further performed and the obtained lattice parameter
values are summarized in Table 1. The refined lattice parameters
are in good agreement with the published results [52]. The
refinement also suggests trace TiO2-B (0.49%) may coexist in the
TiO2 host. SEM result (Fig. 3b) depicts the TiO2 product comprises
porous urchins with uniform particle sizes of 500 nm. These
urchins tend to densely pack together with a higher tap density in
comparison to commercial P25 nanoparticles (Fig. S7). TEM image
in Fig. 3c discloses the TiO2 urchins are constructed from a large
Table 1
Refined unit cell parameters of the as-obtained TiO2 material.
Phases Space group a (nm) b (nm) c (nm) Content (wt%) Rw (%)
anatase I41/amd 0.37807 0.37807 0.95013 99.51 8.98
TiO2-B R-3c: H 0.52406 0.52406 1.35806 0.49 8.98
210 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214
Fig. 4. Nitrogen sorption isotherms and pore size distribution plot (inset) of the
porous TiO2 urchins.
number of interwoven nanochains, forming porous spherical cores
and hairy shells. Each nanochain is comprised of connected 5 nm
nanocrystals. The morphology transformation from titanate nano-
tubes to TiO2 nanocrystals adheres to the local structure
rearrangement of [TiO6] octahedra. The nanotubes with small
diameters can hardly stand the internal strains and become
disconnected during structure reorganization [53]. HRTEM micro-
graph shown in Fig. 3d further depicts a polyhedral anatase
nanocrystal enclosed by (101) and (001) planes (labelled by dashed
square in the middle region and FFT pattern in the inset on top
right). In addition, one TiO2-B (JCPDS card No. 74-1940) [37] grain
is also observed by the HRTEM (labelled by dashed square on the
left bottom) and corresponding FFT pattern (inset on the right
bottom). The coexistence of trace TiO2-B distributed in the anatase
host is believed to improve the Li+ storage capability with
enhanced electron/Li+ transfer capability at the interface of the
two-phase boundaries [19].
The unique porous network might endow the resultant TiO2
material with a high surface area. To this end, nitrogen adsorption-
desorption experiments of the porous TiO2 urchins were mea-
sured. As depicted in Fig. 4, the isotherms can be identified as type
IV with two hysteresis loops. The first loop located at relative
pressures of 0.650.85 is related to the capillary condensation in
the mesopores while the second loop located at relative pressure of
0.91.0 indicates the presence of macropores among adjacent
spheres. The sample yields a high specific surface area of
152 m2 g
1 based on the Brunauer-Emmett-Teller (BET) model.
Pore size distribution centers at ca. 7 nm based on the Barrett-
Joyner-Halenda (BJH) model from the desorption branch, which
apparently agrees with the TEM analysis (Fig. 3c).
Hierarchically porous nanostructures with a high surface area
and pore structures at different length scales may have promising
applications in energy storage and conversion, as well as
environment fields [54]. As a proof-of-concept, we next evaluate
the electrochemical performance of the porous TiO2 urchins as
anode in LIBs. Meantime, we study the structure and morphology
evolution of the TiO2 material upon electrochemical cycling.
The Li+ storage process in TiO2 lattice can be formulated by the
following equation
TiO2 + xLi+ + xe
! LixTiO2 (0  x  1).
Theoretically, the maximum Li+ storage capacity is 335 mA h

1
g when one Li+ is inserted in one TiO2 molecule accompanied by
a complete reduction of Ti4+ to Ti3+. However, the strong
electrostatic repulsion between the inserted Li+ ions results in
the random distribution of them over half of available interstitial
octahedral sites. Therefore, from a practical point of view, the
maximum reversible insertion level is limited to an intercalation
coefficient of 0.5 Li+ per formula unit of TiO2, corresponding to a
reversible capacity of 170 mA h g
1 [3]. Porous TiO2 nano-
structures are expected to possess higher Li+ storage capacity
due to their large contact interface with electrolyte and increased
pseudocapacitive Li+ storage at grain surfaces.
Cyclic voltammograms (CVs) were firstly recorded to study the
reaction kinetics and reversibility of the TiO2 electrode. From
Fig. 5a, a pair of dominant redox peaks (A-peaks) can be observed
at ca. 1.7 V (cathodic sweep) and 2.1 V (anodic sweep) in the first
sweep for the TiO2 electrode. The small overpotential of 0.4 V
signifies the good reaction kinetics of the TiO2 electrode. In the
second cycle, the cathodic peak shifts to 1.67 V while the anodic
peak stays almost unaltered due to an activation process. The third
CV curve almost overlaps with the second one, suggesting the high
reversibility of the electrode in the following sweeps. In addition,
two pairs of extra redox peaks (S1-, S2-peaks) are observed at
1.50/1.55 V (cathodic sweep) and 1.55/1.62 V (anodic sweep),
respectively, which can be attributed to the characteristic peaks of
trace TiO2-B phase [19]. The CV curves were further recorded at
varying scan rates from 0.1 to 1 mV s
1 (Fig. S8a), showing an
increased potential separation of redox peaks due to the
incremental polarization. In addition, the anodic peak currents
of anatase (A-peaks) scale with the square root of scan rates due to
a diffusion-controlled Li+ insertion process (Fig. S8b) [51]. In
contrast, the peak currents of TiO2-B (S1-, S2-peaks) linearly scale
with the first power of scan rates, which is typical of pseudoca-
pacitive Li+ storage process (Fig. S8c) [37,55].
Fig. 5b presents the first two discharge-charge curves of the
porous TiO2 urchins at 0.5 C (1 C = 170 mA g
1). Well-defined
voltage plateaus can be observed at 1.7 V and 1.9 V during
discharge and charge, which are in accordance with the CV
analyses. The Li+ insertion in anatase TiO2 can be divided into three
different stages (regions I, II, and III) [56]. The first stage (region I)
shows a monotonous potential drop from open-circuit potential to
a plateau of 1.7 V, relating to a pseudocapacitive surface effect or
solid-solution insertion mechanism [57]. The second stage (region
II) is characterized by a horizontal plateau region, reflecting the
process of Li+ insertion into the vacant octahedral sites of TiO2
lattice. During this process, a two-phase reaction occurs with
equilibrium between tetragonal Li0.01TiO2 and orthorhombic
Li0.5TiO2 [3]. The third stage (region III) shows a slope potential
drop linking to the Li+ storage at the surface layer of TiO2 grains
[56]. The very long slope region of region III suggests an increased
surface Li+ storage of the porous TiO2 urchins due to their high
surface area and small crystallite size. The initial discharge
capacity of the porous TiO2 urchins is 263.4 mA h g
1 and the
subsequent charge capacity is 196.6 mA h g
1, leading to a
coulombic efficiency (CE) of 75%. The initial irreversible capacity
loss is caused by insertion of Li+ into sites not extractable and
decomposition of trace moisture adsorbed on the electrode surface
[52]. The CE value is increased further to 94.6% in the second cycle,
indicating the fast balance of the Li+ insertion and extraction in the
following discharge-charge process.
The rate capability of the TiO2 material is shown in Fig. 5c. It
reveals the discharge and charge capacities of the TiO2 electrodes
decrease along with the increase of current rates. However, the
porous TiO2 urchins still deliver highly reversible Li+ storage
capacities of 166, 146.1, 123.1 and 94.4 mA h g
1 at 2, 5, 10 and 20 C,
respectively. After lowering the current rate to 0.5 C, the Li+ storage
capacity of the urchins can be recovered to 204 mA h g
1 again. In
comparison, the commercial P25 nanoparticles display an inferior
Li+ storage capacity of 91.4, 69.4 and 39.2 mA h g
1 at 0.5, 1, and 2 C,
respectively. Further, the electrochemical performance of the
porous TiO2 urchins is superior or comparable to an array of TiO2
nanostructures and TiO2/carbon nanohybrids, such as porous
microspheres composed of octahedra (157.3 mA h g
1 at 1 C) [35],
anatase nanosheets with exposed (001) facets (180 mA h g
1 at
 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214 211

Fig. 5. Electrochemical performances of the porous TiO2 urchins and commercial P25 nanoparticles. (a) cyclic voltammetry (CV) curves recorded at 0.1 mV s
1, (b) the first
two discharge-charge curves of the TiO2 spheres at 0.5 C, (c) rate property, and (d) cycling performances, (e) electrochemical impedance spectroscopy data and equivalent
circuit model (inset), (f) long-term cycling performance of the porous TiO2 urchins at 10 C for 5500 cycles. (1 C = 170 mA g
1).

0.5 C and 100 mA h g
1 at 10 C) [10], peapod-like mesoporous TiO2-
C array (164 mA h g
1 at 1 C and 124 mA h g
1 at 10 C) [58], and
mesoporous hollow spheres with conformal carbon coating
(137 mA h g
1 at 5 C) [59]. Fig. 5d further displays the cycling
performance of the TiO2 electrodes at 0.5 C and 1 C, respectively. It
is clear that the porous TiO2 urchins demonstrate high and stable
Li+ storage capacities of 206.2 mA h g
1 and 172.3 mA h g
1 over
100 cycles at 0.5 C and 1 C, respectively, which are much better
than that of commercial P25 nanoparticles and superior to the
mesoporous TiO2 microspheres composed of nanoparticles
(160.5 mA h g
1 after 100 cycles at 1 C) [41].
Electrochemical impedance spectroscopy (EIS) data are per-
formed to give more information on the electrode reaction kinetics
(Fig. 5e and Fig. S9). The EIS responses can be divided into high,
high-to-medium, and low frequency regions, corresponding to the
series resistance (Rs), charge transfer resistance (Rct) at electrode-
electrolyte interface, and Li+ diffusion resistance (W) in the solid
state, respectively [60]. Fig. S9 shows the Nyquist plots of the TiO2
urchins electrode before cycling and after 5 cycles at 0.5 C. The
obvious decrease of Rct after initial cycling can be ascribed to the 3D
interconnected porous structure, which provides a better interface
contact between the active material and electrolyte and thus
reduces the charge transfer resistance. To further confirm that, the
Nyquist plots of the TiO2 urchins and commercial P25 were also
studied and fitted using ZView software based on an equivalent
circuit model shown in the inset of Fig. 5e. It depicts that the two
electrodes have similar Rs values (4 V). However, the electrode
made of porous TiO2 urchins has a much reduced Rct value of
64 V in comparison to that of the P25 electrode (107 V). The
smaller Rct value is a clear indication of much facile charge transfer
occurring at the electrode-electrolyte interface as well as a reduced
total internal resistance in the porous electrode. Moreover, the
larger slope in the Warburg-like response of the electrode made of
porous urchins suggests a more rapid Li+ diffusion in the solid-
state. As a result, the EIS results unravel more effective electronic
and ionic conduction in the porous TiO2 urchins for more efficient
Li+ insertion/extraction.
The long-term cycling performance of the porous TiO2 urchins
is further evaluated at 10 C after activation for two cycles at 0.5 C.
As shown in Fig. 5f, the TiO2 material exhibits an initial capacity of
129.2 mA h g
1 at 10 C and retains a reversible Li+ storage capacity
of 121.8 mA h g
1 over 1000 cycles with 94.3% capacity retention.
Then, the porous TiO2 urchins gradually exhibit slight capacity loss
after each cycle. The Li+ insertion capacity of the porous TiO2
urchins is lowered to 89.1 mA h g
1 after 5500 cycles with 69%
capacity retention.
To probe the possible capacity decay and structure evolution
mechanism of the material, ex-situ XRD, SEM, and TEM character-
izations of the TiO2 electrodes after electrochemical testing for 50
cycles and 5500 cycles were performed, respectively. From XRD
pattern in Fig. 6a, all the visible diffraction peaks can be indexed to
anatase phase in addition to some strong peaks arising from the
212 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214

urchins after 50 cycles largely retain anatase structure, suggesting

the very high reversibility of Li+ insertion/extraction in/from the
anatase lattice at the early stage. In contrast, HRTEM micrograph
(Fig. 7f) reveals the TiO2 electrode after 5500 cycles consists of both
anatase nanocrystals and cubic Li1TiO2 dots (10 nm in size). The
fringe spacing of 0.35 nm and 0.21 nm can be indexed to the
(101) facet of anatase and (200) facet of cubic Li1TiO2 (JCPDS card
No. 016-0223) [61], respectively. The coexistence of TiO2 and
Li1TiO2 can be further verified by the corresponding FFT pattern
(inset in Fig. 7f) derived from the HRTEM micrograph. The TEM
result, together with the high Li+ storage capacity of the porous
TiO2 urchins (Fig. 5), suggests that cubic Li1TiO2 has been reversibly
formed and decomposed during the initial discharge-charge
cycles, leading to increased Li+ storage capability. Then, some of
Li1TiO2 phase formed during discharge gradually evolves into
Fig. 6. Ex-situ XRD patterns of the porous TiO2 urchins after galvanostatic cycling at
isolated nanodots and randomly distributed in the anatase host,
10 C for 50 cycles (a) and 5500 cycles (b), respectively.
which loses electrochemical activity in the subsequent cycling.
To further discern the origin of the trace Li1TiO2 dots, CV curves
underlying Cu current collector, suggesting the reversible Li+
of the porous TiO2 urchins after cycling at 10 C for 5500 times were
storage in the obtained TiO2 material. Compared to Fig. 6a, the TiO2
recorded and compared with that of a fresh TiO2 electrode before
electrode after 5500 cycles displays a slight reduction of diffraction
galvanostatic test. As depicted in Fig. 8, the two CV curves roughly
peak intensity and disappearance of (001) plane (Fig. 6b), which is
overlap with each other, suggesting the high redox reversibility of
an indication of the loss of anatase phase as well as the instability
the obtained TiO2 material. However, the intensity of redox peaks
of active (001) crystal facets of anatase upon electrochemical
for anatase slightly lowers while that for TiO2-B stays the same,
cycling.
implying some anatase has been irreversibly converted into
SEM observation in Fig. 7a, d depicts that the “urchin”
electrochemically inert Li1TiO2 and lost Li+ storage ability in the
morphology has been well retained and the urchins are in intimate
subsequent cycling. In contrast, the trace TiO2-B phase remains
contact without aggregation or cracking during the long-term
electrochemically active even after long-term cycling due to their
electrochemical tests. From the magnified SEM images in the insets
pseudocapacitive Li+ storage characteristics, more open channel
of Fig. 7a and d, it can be found that the nanochains-constructed
structure for Li+ diffusion, and low mass density than anatase,
shells have been largely retained. The high structure stability of the
rendering the formation and decomposition of Li1TiO2 phase more
porous urchins during electrochemical tests can be further
facile and reversible.
confirmed by TEM images (Fig. 7b, e). In particular, some
Based on the above electrochemical and structural data, the
nanocrystals-connected nanochains can still be observed on the
superior electrochemical properties of the porous TiO2 urchins can
outer layer of the urchins. However, HRTEM analyses clearly show
be mainly ascribed to their distinct structural characteristics: (1)
some structure evolution of the porous urchins after different
3D hierarchical porous network with large voids among the
electrochemical cycles. The lattice fringes in the HRTEM micro-
adjacent urchins and mesopores within each urchin is ideal for
graph and corresponding FFT pattern reveal the porous TiO2

Fig. 7. Ex-situ SEM (a, d), magnified SEM (insets of a and d), TEM (b, e) and HRTEM (c, f) micrographs and corresponding FFT patterns (insets of c and f) of the TiO2 urchins after
cycling at 10 C for 50 cycles (a–c) and 5500 cycles (d–f), respectively. The capital letters “T” and “L” in (c) and (f) denote TiO2 and Li1TiO2, respectively.
 Y. Cai et al. / Electrochimica Acta 210 (2016) 206–214
Fig. 8. CV curves of a fresh electrode made of TiO2 urchins recorded in the second
sweep (a) and after galvanostatic cycling at 10 C over 5500 cycles (b). (Scan rate:
0.2 mV s
1).
large electrode/electrolyte interface contact, better electrolyte
permeation and mass transfer; (2) the connected mesochannels
effectively shorten the Li+ and electron diffusion pathways; (3) the
nanochains and straight pore channels efficiently buffer the minor
volume change during (de)lithiation; (4) the coexistence of trace
TiO2-B nanophases marginally increases the Li+ storage capacity
and improve the charge transfer/transport at two-phase bound-
aries.
However, the porous TiO2 urchins also exhibit slight capacity
loss after very long-term electrochemical cycling possibly due to
the irreversible formation of trace isolated Li1TiO2 nanodots. It is
noted that part of the obtained TiO2 material can be fully lithiated
into Li1TiO2 due to its unique porous and nanocrystalline
characteristics of the porous urchins during the initial electro-
chemical cycling. However, some Li1TiO2 phase formed during
discharge gradually loses electrochemical reactivity and exists as
isolated nanodots randomly distributed in the TiO2 host in the later
recharge process during the long-term cycling. This fact is probably
due to either the sluggish Li+ diffusivity of Li1TiO2 [62] or
insufficient electronic wiring of the Li1TiO2 nanodots with
surrounding electrode matrix [63]. In addition, the adjacent TiO2
nanochains might gradually fuse together during (de)lithiation,
leading to the loss of some straight mesochannels and increase of
Li+ concentration gradient between the outer and inner of the
porous urchins. However, no cracks or larger secondary particles
are observed in our material even after very long-term electro-
chemical cycling [45], demonstrating the very high structure
integrity of the porous TiO2 urchins.
4. Conclusions
Porous TiO2 urchins with spherical cores and nanochains-
constructed shells have been fabricated using TiO2/oleylamine as
precursor. The resultant TiO2 material exhibits superior electro-
chemical performance with a combination of high capacity,
superior rate capability and excellent cycling stability. This
improved electrochemical performance of the TiO2 material can
be attributed to their distinct pore structures and high structure
stability. More importantly, ex-situ structure characterizations
demonstrate the irreversible transformation of trace anatase
nanocrystals into cubic Li1TiO2 nanodots, which explains the
slight capacity decay of the porous TiO2 material after long-term
cycling. Further work is in progress to further optimize the
geometry and pore structure of the TiO2 material for more stable
cycling stability. In addition, the porous TiO2 urchins and
(protonated) titanates may find potential applications in sensitized
solar cells, (photo)catalysis, and sorption.
213
Acknowledgements
This work is realized in the frame of a program for Changjiang
Scholars and Innovative Research Team (IRT_15R52) of Chinese
Ministry of Education. B. L. Su acknowledges the Chinese Central
Government for an “Expert of the State” position in the Program of
the “Thousand Talents”. H. E. Wang and Y. Li acknowledge the
Hubei Provincial Department of Education for the “Chutian
Scholar” program. H. E. Wang also thanks the financial support
from National Natural Science Foundation of China for Young
Scholars (No. 51302204) and China Scholarship Council (CSC) for
supporting as a Visiting Scholar at University of Washington,
Seattle, WA, US. W. J. Zhang thanks the financial support from the
Applied Research Grant of the City University of Hong Kong (ARG
9667111).
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.2016.05.140.
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