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N-doped TiO2 nanotubes/N-doped graphene

nanosheets composites as high performance
Cite this: J. Mater. Chem. A, 2014, 2,
15473 anode materials in lithium-ion battery†
Published on 25 July 2014. Downloaded by Ege Universitesi on 03/09/2015 09:25:07.

Yueming Li,*a Zhiguang Wanga and Xiao-Jun Lv*b

Received 8th June 2014
Accepted 24th July 2014
DOI: 10.1039/c4ta02890b
www.rsc.org/MaterialsA
To improve the electrochemical performance of TiO2 nanotube as anode materials in Li-ion batteries,
N-doped TiO2 nanotube/N-doped graphene composites were prepared via hydrothermal synthesis
followed by heat treatment in the presence of urea. The N-doped TiO2 nanotubes/N-doped graphene
composites were characterized by X-ray powder diffraction, transition electron microscopy, scanning
electron microscopy and X-ray photoelectron spectroscopy. The electrochemical experiments
demonstrated that the as-prepared sample exhibit superior discharge capacity (up to 369 mA h g
1 at
0.1 A g
1) as well as excellent rate ability (90 mA h g
1 even at 5 A g
1 at 180th cycle) as anode materials
in lithium-ion batteries.

Although the TiO2 electrode is safe, the poor electronic

Introduction
The rechargeable Li-ion battery has become one kind of domi-
nant battery that powers most of today's portable electronics,
due to its high performance characteristics, such as high
voltage and long cycle life.1,2 However, some big challenges
remain in safety and quick charge–discharge ability for the
Li-ion battery. As is known, the widely used anode material in
commercial Li-ion battery is graphite. One concern for graphite
is its low discharge potential, which may cause the decompo-
sition of the organic electrolyte and thus result in a serious
incident.3 In addition, most of the state-of-the-art novel anode
materials in lithium batteries, like Si and SnO2, still suffer from
insufficient rate performance and short cycle life.4 It is quite
urgent to develop high performance anode materials with high
safety.5
TiO2, an extensively used material, has been thought as one
of the ideal anode materials for Li-ion battery; it has a much
improved safety performance due to its high discharge plateau
potential (about 1.5–1.8 V versus lithium) that would not
decompose the organic electrolyte.6,7
a
State Key Laboratory of Metastable Materials Science and Technology, College of
Materials Science and Engineering, Yanshan University, Qinhuangdao, Hebei
Province, 066004, China. E-mail: liyueming@ysu.edu.cn
b
Key Laboratory of Photochemical Conversion and Optoelectronic Materials and HKU-
CAS Joint Laboratory on New Materials, Technical Institute of Physics and Chemistry,
Chinese Academy of Sciences, Beijing 100190, P.R. China. E-mail: xjlv@mail.ipc.ac.cn
† Electronic supplementary information (ESI) available: Fig. S1 (HRTEM of
TiO2/graphene and N-doped TiO2 nanotube/graphene nanosheets); Fig. S2 (XPS
survey spectrum of N-doped TiO2/N-doped graphene nanosheets) and Fig. S3
(The 40th charge–discharge curves of TiO2/graphene and N-doped TiO2
nanotube/graphene nanosheets at current density of 100 mA g
1). See DOI:
10.1039/c4ta02890b
conductivity and the low Li-ion diffusion ability of TiO2 would
limit its quick charge–discharge ability as an anode material,
which is of great importance for the application in high power
appliances, such as electric vehicle (EV). Up to now, various
efforts have been made to improve the electronic conductivity
and/or Li-ion diffusion ability of TiO2. One proposed strategy
has been to coat conductive materials, such as carbon materials
or RuO2, on the interior or exterior surface of TiO2 to increase its
electronic conductivity.7,8 The RuO2 coating is very limited due
to its high price and toxicity. Compared with RuO2 coating,
carbon coating provides a cheap and effective method to
increase the conductivity of TiO2.9,10
Among carbon materials, two-dimensional graphene has
proved a very effective material to improve the conductivity and
electrochemical performance of electrode materials/carbon
composites due to its high conductivity and large surface area
based on our previous work and the work of others.11 Another
strategy to improve the electrochemical performance of TiO2 is
to decrease the particle size because nanostructured materials
can facilitate the Li-ion diffusion in electrodes by shortening the
Li-ion insertion/extraction pathway.12 Thus, TiO2 nanoparticles,
nanowires and nanotubes have been studied as anode materials
in Li-ion battery.13,14 Furthermore, the electrochemical perfor-
mance of TiO2 is also dependent on its crystalline phase and
chemical doping.15 For example, nitrogen doping has been
proven to be an effective strategy for improving the capacity of
TiO2.16–19 In addition, it has also been proven that chemical
doping of nitrogen is an effective method to improve the elec-
trochemical performance of carbon materials, such as graphene
nanosheets as the nitrogen atom can alter the electronic and
chemical properties due to its comparable atomic size and ve

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Journal of Materials Chemistry A
valence electrons that are available to form strong valence
bonds with carbon atoms.20–25
Based on above analysis, the combination of N-doped
nanostructured TiO2 and N-doped graphene would improve the
electrochemical performance of TiO2. However, to the best of
our knowledge, there are no such reports on composites of
N-doped nanostructured TiO2 on the surface of N-doped gra-
phene nanosheets as an electrode for a Li-ion battery.
In this study, we have synthesized N-doped TiO2 nanotubes
on the surface of N-doped graphene using urea as the nitrogen
source, in which both TiO2 and graphene nanosheets were
doped by nitrogen at the same time during the decomposition
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of urea under heat treatment. The decomposition of urea
entered not only into the lattice of TiO2 but also into the skel-
eton of graphene nanosheets. Electrochemical experiments
showed that the as-prepared N-doped TiO2 nanotubes/N-doped
graphene composites exhibited excellent electrochemical
performance as the anode material in a Li-ion battery.
Experimental
Materials
TiO2 nanoparticles and graphite powder (325 mesh) were
obtained from Alfa Aesar. All other reagents were of analytical
grade and used without further purication except otherwise
stated.
Synthesis of N-doped TiO2/N-doped graphene nanosheets
To prepare N-doped TiO2 nanotubes/N-doped graphene nano-
sheets, TiO2 nanotubes/graphene nanosheet composites were
rst prepared according to previous reports, with modica-
tions.26 The typical procedure was as follows. First, 140 mg
graphite oxide and 1 g TiO2 nanoparticles was sonicated in
55 mL of DI water for 2 h. Then, 22 g NaOH was added, and
mixture was transferred to a Teon-lined stainless steel auto-
clave. The mixture was then heated at 150  C for 40 h, and TiO2
nanoparticles were transformed to titanate nanotubes during
this process. The black-gray precipitates were ltered several
times with deionized water. Further, the resulting precipitates
were added to a 0.1 M HCl solution under stirring for 12 h. The
nal product was washed with DI water until the ltrate became
neutral and dried at 60  C. To prepare N-doped TiO2/N doped
graphene, the as-prepared product was heated at 400  C for 2 h
in presence of urea (urea : TiO2/graphene ¼ 2 : 1 mass ratio)
under an Ar atmosphere. TiO2 nanotubes formed due to the
removal of water in the titanate nanotubes during heat treat-
ment. Undoped TiO2/graphene composites were prepared
according to above procedure, except that no urea was intro-
duced during heat treatment at 400  C. For comparison, TiO2
nanotubes were also prepared with a similar procedure except
that no graphite oxides were added during hydrothermal
synthesis and no urea was added during heat treatment.
Characterization
The powder X-ray diffraction (XRD) measurements of the
samples were recorded on a D-max 2500 X-ray powder
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diffractometer using a graphite monochromator with Cu Ka
radiation (l ¼ 1.5406 Å). Data were collected between scattering
angles (2q) of 5 –80 at a scanning rate of 4 min
1. Thermog-
ravimetric analysis (TG) measurements were performed in
NETZSCH5 STA 449C thermogravimetric analyzer at a heating
rate of 5  C min
1 under air atmosphere from room tempera-
ture to 800  C. TEM specimens were prepared by drop-casting
the as-prepared sample dispersions onto carbon-coated TEM
grids and dried in air. JEM 2010 transition electronic micros-
copy was used for TEM analysis. X-ray photoelectron spectros-
copy (XPS) was carried out on a PHI Quantera; binding energy
was calibrated with C1s ¼ 284.8 eV.
Electrochemical performance
To evaluate their electrochemical performance as the anode
material in Li-ion batteries, the electrodes were constructed by
mixing the active materials, conductive carbon black and poly-
vinylidene uoride (PVDF), in the weight ratio 80 : 15 : 5. The
mixture was prepared as a slurry in N-methyl pyrrolidinone and
spread onto copper foil using the doctor blade technique. The
electrodes were dried under vacuum at 120  C for 12 h. The cells
were assembled inside the argon-lled glove box (Braun, H2O <
1 ppm and O2 < 1 ppm) 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 a 1 : 1 volume ratio ethylene carbonate (EC) : dimethyl
carbonate (DMC) solvent. Assembled cells were allowed to soak
overnight and tested on a BT 2000 battery testing unit (Arbin,
USA). The galvanostatic charge and discharge of the assembled
cells were tested at varied current densities between the voltage
limits of 1 and 3 V (vs. Li) at room temperature. The specic
capacity of pure TiO2 nanotubes was calculated based on the
mass of TiO2, while those of the composites were calculated
based on the total mass of (N-doped) TiO2/graphene nanosheet
composites.
Results and discussion
As shown in Fig. 1, there is a characteristic peak at 10.8 (cor-
responding to 0.9 nm of interplanar spacing) in the XRD pattern
of graphite oxide, indicating the successful oxidation of the
graphite. The extended interplanar spacing facilitates the
exfoliation of GO in the aqueous solution. Fig. 1b shows the
XRD pattern of the TiO2 nanotubes. Most of the strong peaks
can be easily indexed to anatase-phase TiO2 (JCPDS no. 21-1272)
and the remaining weak peaks can be indexed to the TiO2 (B)
phase (JCPDS no. 46-1238). For the composites of TiO2/gra-
phene nanosheets and N-doped TiO2/graphene, the disappear-
ance of the diffraction peak at 10.8 indicates the successful
reduction of GO to graphene nanosheets, shown in Fig. 1c and
d. Furthermore, the TiO2/graphene and N-doped TiO2/graphene
shows characteristic peaks of both anatase and TiO2 (B).
Compared with pure TiO2 nanotubes, the relative intensity of
the characteristic peaks at 36 –38 assigned to anatase
decreased for these two samples, indicating an increase of the
TiO2 (B) phase contents. Notably, the characteristic peak for
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Fig. 1XRD patterns of graphite oxide (a), TiO2 nanotubes (b), TiO2
nanotubes/graphene composites (c) and N-doped TiO2 nanotubes/N-
doped graphene nanosheets composites (d) (* TiO2-B phase).
graphene nanosheets is expected at about 26 (002), which is
difficult to identify due to the weak intensity compared with the
dominant TiO2 and because it overlaps with TiO2 as well. In
addition, the broadened peaks at 26 for N-doped sample may
be related to distortion in the O–Ti–O lattice due to the doping
of nitrogen into TiO2.27,28
Fig. 2(A) shows the SEM image of TiO2 nanotubes, which are
composed of entangled one-dimensional nanostructures with
diameters of several nanometers and length up to several
hundred nanometers. The morphology of TiO2 in the compos-
ites is similar to that of as-prepared pure TiO2 nanotube. Aer
nitrogen doping, most TiO2 kept nanotube morphology, while
the increased degree of agglomeration can be seen, which may
be owing to changed reaction conditions caused by the intro-
duction of urea.29,30 However, the graphene nanosheets in the
composites are not distinct due to their low contrast in SEM.
Thus, TEM was used to further clarify the structure of the
composites. It is clearly visible that lots of TiO2 nanotubes,
SEM images of TiO2 nanotube, (A) TiO2 nanotube/graphene
Fig. 2
composites (B) and (C) N-doped TiO2/N-doped graphene nanosheets
composites at low magnification (C) and at high magnification (D).
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which showed the typical hollow tubular morphology are
located on the surface of two-dimensional graphene nano-
sheets, while the distribution of TiO2 nanotubes on graphene is
not uniform, as shown in Fig. 3(A) and (B). Furthermore, it can
be seen that some randomly oriented TiO2 nanotubes lie
parallel to the graphene surface, similar to previous reports.7
Nitrogen doping seemed to have little effect on morphology
through TEM observation, though it can be observed the
increased degree of aggregation via SEM. The TiO2 nanotubes or
N-doped TiO2 nanotubes have a typical diameter of about 7–10
nm and can be up to 1 micrometer in length, and the wall
thickness of nanotube is about 2–3 nm. Moreover, as shown in
Fig. S1,† the lattice spacing of the N-doped TiO2 nanotube
derived from the HRTEM image is about 0.61 nm, corre-
sponding to the interplanar distances of (001) planes of TiO2
(B), indicating the presence of TiO2 (B).
The XPS survey spectra of the N-TiO2/graphene composite
conrmed the presence of C, O, Ti and N elements, as shown in
Fig. S2.† In high resolution XPS spectrum of Ti 2p (Fig. 4A), the
Ti 2p3/2 and Ti 2p1/2 peaks are located at binding energies of
459.1 and 464.8 eV, respectively, which is in agreement with the
value of Ti4+ in the TiO2 lattice.31 The spectrum of the experi-
mental O1s band obtained for N-doped samples (Fig. 4B) can be
convoluted into two components at 530.5 (main peak) and 531.8
eV corresponding to O2
in TiO2 lattice and the residual oxygen-
containing groups in graphene.32 The high-resolution C1s peak
(Fig. 4C) was centered at 284.8 eV, and the tail at higher binding
energies indicated the existence of carbon atoms connected to
N and O heteroatoms.33 The peak can be tted to four peaks.
The main peak observed at 284.8 eV can be assigned to C]C
bonds, the peak at 285.6 eV assigned to C]N & C–O, the peak at
Fig. 3 TEM images of TiO2 nanotube/graphene composites (A) at low
magnification and (B) at high magnification, N-doped TiO2 nanotubes/
graphene composites (C) at low magnification and (D) at high
magnification.
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Journal of Materials Chemistry A
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Fig. 4 High resolution XPS spectra (Ti 2p, O1s, C1s and N1s) of N-
doped TiO2 nanotubes/N-doped graphene nanosheets.
287 eV assigned to C–N & C]O, and the peak at 289 eV assigned
to N–C]O. The broad N1s XPS peak of the N-doped sample
(Fig. 4 D) can be tted to the ve peaks of Ti–N (396.0 eV),
pyridinic N (398.2 eV), pyrrolic N and O–Ti–N (399.6 eV),
graphitic N (401.0 eV) and C–N–O (402.8 eV), indicating the
successful doping of nitrogen atoms into the TiO2 lattice as well
as into the graphene framework.33–35 The amount of N element
is about 2% (mass ratio) based on the XPS experiment.
To quantify the mass percentage of TiO2 in the composites,
the as-prepared composites were analyzed by TG at a rate of 5  C
min
1 in air. As shown in the TG curve (Fig. 5), the mass
percents of TiO2 in TiO2 nanotube/graphene and N-doped TiO2/
graphene are 90.1% and 89.7%, respectively, indicating that the
mass percent of graphene is about 10% for both sample.
Fig. 6(A–C) shows the cyclic voltammogram of TiO2 nano-
tube, TiO2/graphene and N-doped TiO2/graphene nano-
composites. An obvious pair of peaks is observed at about 2.1 V
(Li-ion extraction) and 1.7 V (Li-ion insertion) in the CV curve of
TiO2 nanotubes, which is common for the anatase phase. One
Fig. 5 TG curve of TiO2 nanotubes/graphene nanosheets and N-
doped TiO2 nanotubes/N-doped graphene nanosheets under an air
atmosphere.
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Fig. 6 CV curves of TiO2 nanotube (A), TiO2 nanotube/graphene (B)
and N-doped TiO2 nanotubes/N-doped graphene nanosheets elec-
trodes (C); charge–discharge curves of TiO2 nanotube (D), TiO2
nanotubes/graphene (E) and N-doped TiO2 nanotube/N-doped gra-
phene nanosheets electrodes (F).
pair of inconspicuous peaks at 1.7 and 1.5 V indicates the
presence of the TiO2 (B) phase,36 which is consistent with the
XRD analysis. The one pair of broad reversible pseudocapacitive
peaks at 1.7 and 1.5 V become predominant for TiO2/graphene
or N-doped TiO2/graphene, in addition to the ordinary peaks
(2.1 and 1.7 V) assigned to the anatase phase, indicating the
increased TiO2 (B) content aer combination with graphene
nanosheets. Notably, there are some decreases either in the
cathodic or anodic current in the second cycle in CV for all the
samples, indicating that the irreversible capacity losses have not
been totally eliminated. Fig. 6(D–F) presents the discharge and
charge voltage proles of as-prepared TiO2 electrodes at current
density of 0.1 A g
1.
The pure TiO2 nanotube electrode exhibited a long and at
charge–discharge potential plateau at about 2.1 and 1.7 V,
which is consistent with the redox peaks in the cyclic voltam-
mogram. Aer the introduction of graphene nanosheets, it can
be seen that the TiO2/graphene and N-doped TiO2/graphene
electrodes exhibit a short discharge potential plateau at about
1.7 V, followed with a long sloping curve from 1.7 to 1.0 V. The
pure TiO2 nanotube can deliver a capacity of only 200 mA h g
1
at the current density of 0.1 A g
1 for the rst discharge, while
the rst discharge capacity of TiO2/graphene and N-doped
TiO2/graphene increase to 354 and 369 mA h g
1, respectively,
shown in Fig. 6(E, F). Even aer 40 cycles, the TiO2/graphene
and N-doped TiO2/graphene still delivered a discharge capacity
of 197 and 232 mA h g
1, as shown in Fig. S3.† However, the
irreversible capacity did not show an obvious decrease aer
introduction of graphene or through N-doping. The irreversible
capacity mainly results from the interfacial reaction between
TiO2 and the electrolyte involved in the forming of a solid
electrolyte interface (SEI) lm, which is very common to lithium
intercalation host materials.4,37–40 Considering the superior
performance at low current density for the TiO2/graphene
electrode, high current densities were explored to study the rate
capability. Thus, aer the cell cycled for 40 cycles, the same
cell was further charged and discharged at progressively
higher rates for an additional 140 cycles. These results are
shown in Fig. 7.
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Fig. 7(A) displays the typical charge and discharge curves of
the N-doped TiO2/N-doped graphene electrode at varied current
densities, presenting a discharge characteristic of TiO2 (B)
phase (long sloping curves with no plateau). As shown in
Fig. 7(B), although the discharge capacity declines at high rates,
the rate retention is excellent. For example, the electrode can
deliver a discharge capacity of 169 mA h g
1 at 1 A g
1 (6C), 148
mA h g
1 at 2 A g
1 (12C) and 126 mA h g
1 at 3 A g
1 (18C).
Even at a high current density of 5 A g
1 (30C) at the 180th cycle,
the composites electrode could deliver a specic capacity of
90 mA h g
1, suggesting excellent rate capability as well as good
cycle performance. The discharge capacity is much higher than
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recently reported CNT/TiO2 composites (about 100 mA h g
1 at
1 A g
1),41 N-doped porous TiO2,19 and the TiO2 nanowire array
in our previous work.37
Because TiO2 nanotubes grew on the surface of graphene
nanosheets, their close contact leads to a much easier electron
transfer due to the excellent conductivity of graphene.
Furthermore, the nanotube morphology makes the transport
lengths for both electronic and Li+ transport in the composites
shorter, facilitating the charge–discharge process. The TiO2 (B)
phase in the N-doped sample provides more open channels,
facilitating the faster transport of Li-ion, resulting better rate
performance.42,43 In addition, the TiO2 nanotubes can act as
Fig. 7(A) Charge–discharge curve N-doped TiO2 nanotube/N doped
graphene at varied current density; (B) cycle performance of TiO2
nanotubes, TiO2 nanotubes/graphene nanotubes and N-doped TiO2
nanotubes/N-doped graphene nanosheets.
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spacers to separate single graphene nanosheets, thereby
helping to preserve the excellent properties of graphene.
Compared with the TiO2/graphene sample, the N-doped
sample exhibited superior electrochemical performance, indi-
cating that the nitrogen doping into the TiO2 lattice and
framework of graphene nanosheets has played a critical role in
improving the electrochemical performance. The nitrogen
doping can improve the electric conductivity as well as the ionic
conductivity, helping to enhance the electrochemical perfor-
mance.34,44 Aer introducing the N atoms, the distortion of Ti–O
lattice may affect the electrochemical reactions on the inter-
faces between electrodes and the electrolyte, as well as Li+ ion
diffusion in the Ti–O lattice. Although the mechanism of the
effects of N-doping on TiO2 should be further studied, the
present experiments have proved that the as-fabricated N-doped
TiO2 nanotube/N-doped graphene nanosheet electrode
possesses excellent electrochemical performance as an anode
material in a Li-ion battery. The results may be further improved
if the electrodes were optimized by engineering of the electrode
structure.45
The electrochemical impedance spectroscopy was also used
to evaluate the electrochemical performance of the as-prepared
samples. As shown in Fig. 8, the Nyquist plots of all the three
samples have shown the typical characteristics of one semicircle
in middle-high frequency range and a sloping straight line in
the low frequency. The semicircle in the middle frequency range
indicated the charge-transfer resistance, relating to the charge
transfer through the electrode/electrolyte interface.
As seen from the Nyquist plots, it can be found that the
radius of the semicircle of N-doped TiO2/N-doped graphene
composites electrode is the smallest and that of the TiO2
nanotubes is the largest among the three samples. The smaller
the radius of semicircle, the smaller the charge transfer resis-
tance. The resistances were calculated on the base of tting
circuit (inset of Fig. 8) using Zsimpwin program. The smaller
semicircle of N-doped TiO2/N-doped graphene electrode indi-
cated its smaller charge transfer resistance (Rct) (about
50.4 ohms), which is much smaller than that of TiO2 nanotubes
Fig. 8 Electrochemical impedance spectra of TiO2 nanotubes, TiO2
nanotube/graphene and N-doped TiO2 nanotube/N-doped graphene
(inset: the fitting circuit, Rs: resistance of the electrolytes; Rct: charge
transfer resistance; Zw: Warburg resistance; Q: constant phase
element).
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Journal of Materials Chemistry A
(220 ohms). This experiment demonstrated that the charge-
transfer resistance of TiO2 electrode can be lowered through
doping the N-atoms into TiO2 and combination with N-doped
graphene nanosheets.
Conclusions
Composites of N-doped TiO2 nanotubes on the surface of N-
doped graphene nanosheets have been successfully prepared.
Electrochemical experiments showed that N-doped TiO2 nano-
tubes/N-doped graphene nanosheets exhibit high specic
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capacity as well as excellent rate performance as an anode
material in the Li-ion battery. During the doping process,
nitrogen entered both into the structure of graphene nano-
sheets and the TiO2 lattice, leading to superior electrochemical
performance. The as-prepared sample not only exhibited very
excellent rate performance but also showed good cycle stability,
suggesting a very promising future in high-performance Li-ion
batteries.
Acknowledgements
This work was nancially supported by NSFC (Grant no.
51202212, 21107117), Natural Science Foundation of Hebei
province (Grant no. E2014203033), Beijing Natural Science
Foundation (Grant no. 2132057).
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