Published in completed and revised form in Chemistry – a European 1
Journal DOI: 10.1002/chem.201303283, Copyright Wiley VCH 2
3
Mesoporous anatase TiO2 nanorods as thermally robust 4
anodes for Li-ion batteries – a detailed insight into 5
formation mechanism 6
7
Gulaim A. Seisenbaeva[a]*, Jean-Marie Nedelec[b,c], Geoffrey Daniel[d], Carmen 8
Tiseanu[e,f], Vasile Parvulescu[e], Vilas G. Pol[g], Luis Abrego[g], Vadim G. Kessler[a]* 9
10
╫ Department of Chemistry, Biocenter, SLU, Box 7015, SE-75007, Uppsala, Sweden; ╩ 11
Clermont Université, ENSCCF, Institut de Chimie de Clermont-Ferrand, BP 10448, F-12
63177 Clermont-Ferrand, France, † CNRS, UMR 6296, ICCF, F-63171 AUBIERE, 13
France, φ Department of Forest Products/Wood Science, SLU, Box 7008, 75007 Uppsala, 14
Sweden, � National Institute for Laser, Plasma and Radiation Physics, P.O.Box MG-36, 15
RO 76900, Bucharest-Magurele, Romania, ‡ Department of Chemistry, Univ. Bucuresti, 16
B-dul Regina Elisabeta, nr. 4-12, Sector 3, 030018 Bucuresti, Romania, 17
╪Electrochemical Energy Storage Department, Chemical Sciences and Engineering 18
Division, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL 60439, USA 19
20
Abstract 26
Uniformly mesoporous and highly thermally robust anatase nanorods were produced with 27
quantitative yield by a new simple and efficient one-step approach. The mechanism of 28
this process was revealed via insertion of Eu3+ cations from the reaction medium as 29
luminescent probe. The obtained structure displays unusually high porosity and active 30
surface area of about 300 m2/g making this material attractive as an anode electrode for 31
Li-ion batteries with specific capacity of 167 mAh/g at C/3 rate. An additional attractive 32
feature is its remarkable thermal stability – heating to 400°C results in decrease of the 33
active surface area to a still relatively high value of 110 m2/g with conservation of open 34
mesoporosity. Thermal treatment at 800°C or higher, however, causes transformation into 35
a non-porous rutile monolith as it commonly observed with nano-titania. 36
37
Keywords : Mesoporous titania, Anatase, Formation mechanism, Thermal stability, 38
Electrochemical performance, Li-ion battery 39
1. Introduction 40
Rational design of more efficient devices for energy storage is one of the most important 41
quests set for modern materials science.1 Li-ion batteries are broadly recognized as one of 42
the most attractive answers to this quest,2-4 combining such attractive features as 43
generally high capacity and low weight and volume, permitting the creation of small and 44
highly efficient energy sources. The key to building up an attractive battery is the design 45
of electrode materials. The matrix for incorporation of Li-ions needs to be thermally and 46
chemically stable, have relatively low density (and molecular mass per unit) and, of 47
course, display high capacity in relation to the stored charge in combination with rapid 48
charging-up kinetics. Among materials, potentially capable to meet these challenges, an 49
important place is occupied by the titanium dioxide5,6. All the crystalline modifications of 50
TiO2 in nano form such as nanoparticles,7 nanotubes,8 nanowires9 and nanoribbons10 were 51
considered as prospective for application as anodes for the Li-ion batteries. They have 52
revealed, however, also certain disadvantages such as poor electron conductivity because 53
of potential aggregation and microsintering of the nanopowders together with poor 54
contact between individual particles and low packing density as discussed in5. Solutions 55
to these problems were sought in application of easily packed microparticles with 56
improved contacts between nano building blocks in their structure11,12. Relatively 57
complex technical solutions for preparation of spherical nanostructured microparticles 58
involving template synthesis in combination with spray-drying have been proposed 59
offering TiO2 with high capacity and superior rate performance with 165 mAh g−1 at 60
10°C and 116 mAh g−1 at 60°C 5. For enhancing electronic conductivity, the autogenic 61
technique was used to synthesize carbon encapsulated, anatase (TiO2–C) anode 62
nanoparticles for lithium-ion batteries, providing a reversible capacity of 200mAhg 63
with C/17 rate 13. 64
We have recently reported an extremely facile rapid hydrothermal synthesis approach 65
based on quick immersion of solid crystalline titanium alkoxide precursors such as 66
commercially available titanium methoxide into boiling water.14 In the present work we 67
have applied the in situ doping of the thus forming nanostructure with Eu3+-cations in 68
order to produce advanced insight into the mechanism of this process and get better 69
understanding for the structural transformation of this nanomaterial in the course of 70
thermal treatment and its functioning as an anode for Li-ion batteries. 71
72
2. Experimental section 73
The synthetic procedure for anatase nanorods has been described by us recently 74
elsewhere. 14 In a typical experiment about 1 g of titanium methoxide, Ti(OCH3)4 75
(Aldrich [992-92-7], Cat. No. 463582), was quickly immersed into 50 ml of water 76
brought to boiling and the mixture was then kept on stirring and boiling in an open air for 77
30 min. It was then cooled down to the room temperature and the product, separated by 78
decantation was dried in air at room temperature. 79
SEM-EDS studies were carried out with a Hitachi TM-1000-μ-DeX tabletop scanning 80
electron microscope. TEM investigations was made using CM12 transmission electron 81
microscope (Philips, Holland) with an accelerating voltage of 100 kV. X-ray powder 82
patterns were obtained using a Bruker SMART Apex-II diffractometer operating with 83
MoKα radiation (λ = 0.71073 Å). Bruker Apex-II and EVA software were used for 84
integration and data treatment. Textural characteristics (specific surface area, mean pore 85
size, porous volume) were measured using nitrogen sorption at 77 K on a Quantachrome 86
Autosorb 1 apparatus. 87
The photoluminescence (PL) measurements were carried out using a Fluoromax 4P 88
spectrofluorometer (Horiba) operated in both the fluorescence and the phosphorescence 89
mode. The repetition rate of the xenon flash lamp was 25 Hz, the integration window 90
varied between 300 ms and 3 s, the delay after flash varied between 0.03 and 3ms, and up 91
to 100 flashes were accumulated per data point. The slits were varied from 0.1 nm to 10 92
nm in excitation as well as emission. Time resolved emission spectra (TRES) were 93
recorded using a wavelength tunable NT340 Series EKSPLA OPO (Optical Parametric 94
Oscillator) for samples excitation at 340-360 nm, 457, 488, 460 - 470, and 514 nm 95
operated at 10 Hz as excitation light source and an intensified CCD camera (Andor 96
Technology) coupled to a spectrograph (Shamrock 303i, Andor) as detection system. The 97
TRES were collected using the box car technique. The initial gate delay, (delay after laser 98
pulse, δt) was set to 1 µs and the gate width δt was varied between 10 to 100 µs. The 99
number of accumulations per pulse laser was varied form 50 up to 500. The PL was 100
detected in the spectral range of 500 nm < λem < 750 nm with a spectral resolution of ~0.3 101
nm. PL decays were measured either by using the “decay by delay” feature of the 102
phosphorescence mode of Fluormax 4P either by integrating the time-resolved emission 103
within certain wavelengths interval. The PL decays were analyzed by fitting with a 104
multi-exponential function f(t) using the commercial software (OriginPro 8): f (t) =∑ Ai 105
exp(− t/τi )+ B (Eq.1), where Ai is the decay amplitude, B is a constant (the baseline 106
offset) and τi is the time constant of the decay i. The average PL lifetime was calculated 107
as amplitude-weighted using the formula: ∑∑
=
ii
iii
A A
Aττ . 108
3. Results and discussion 109
Rational design of titania nanostructures represents one of the most importat challenges 110
in the modern physical chemistry. 15 Recent efforts in the development of titania-based 111
anode materials for Li-ion batteries have been concentrated on several promising tracks: 112
in addition to the already mentioned mesoporous architectures, 11,12 arising from 113
macromolecular templation, and the surfactant-free long-time hydrothermal approaches 114
commonly followed by firing, 16 the techniques involving agents facilitating 115
crystallization, such as fluoride ions have been employed. 17 It has also been noticed that 116
especially nanorod and nanobelt micro morphologies were beneficial for the performance 117
and stability of the titania anodes. 18,19 Even the amorphous nanorods were showing good 118
performance, demonstrated recently for Na-ion batteries. 20 In a number of cases the 119
introduction of conductive filler like graphite or, especially, graphene or graphene oxide 120
18,19,21,22 appeared extremely beneficial, possibly, due to improvement of the electric 121
contacts between the oxide grains. Even after the removal of the carbonaceous template, 122
like in the cases, where collagen fibers of paper filter materials were used to insure 123
nanorod-like morphology, the material remained more efficient and robust in its 124
electrochemical performance. 19,23 125
It was thus plausible that creation of a stable nanorod morphology could act as key factor 126
in producing an efficient TiO2-anode. In the view of the earlier observed topotactic 127
transformation of solid metal alkoxides into highly porous mesostructured 128
nanoarchitectures when the precursors were immersed into boiling water, it appeared 129
attractive to investigate the mechanism of this transformation. It appeared also highly 130
realistic that obtaining such porous nanorod constructions could offer an attractive and 131
very facile approach to highly stable performant, and, due to their high crystallinity, also 132
highly stable anode materials for Li-ion batteries. 133
The material investigated in this work was produced by an extremely simple one-step 134
approach using just a short time boiling in pure water of a metal-organic precursor – 135
titanium methoxide that naturally crystallizes in the form of nanorods. This technique 136
provides easily packed TiO2 nanorods composed of strongly aggregated fully crystalline 137
anatase nanoparticles (Fig. 1) through topotactic hydrolytic transformation14 of the 138
precursor alkoxide crystals. 139
140
[Fig 1] 141
142
In order to provide deeper insight in the formation mechanism of these nanostructures we 143
have carried out an attempt to dope the material with Eu3+-cations to be used as 144
luminescence probe. Insertion was carried out via hydrolysis of precursor using aqueous 145
solution of europium nitrate with the total amount corresponding to 2 mol% content in 146
relation to the sum of cations. The doping did not influence the general appearance of the 147
samples in SEM. XRD showed the presence of anatase as the only distinguishable 148
crystalline phase. Figure 2 illustrates the emission and excitation properties of the non-149
heated and 500 °C heated Eu doped TiO2. From the relative intensities of the broad titania 150
absorption band at ~ 340 nm and f-f absorption lines of Eu measured before and after 151
heating to 500°C, it appears that the titania sensibilization of europium emission is 152
practically absent, although some tiny enhancement was observed for the non-heated 153
sample relative to the heated one (Figure FS1, Upper Inset). 154
155
[Fig 2] 156
157
The non-heat-treated samples displayed rather low degree of sensibilization for the 158
europium bands compared to Eu:TiO2 produced by conventional sol-gel technology 24, 159
indicating that the degree of substitution for Ti atoms in the structure was minor, much 160
less than the total content of the introduced dopant (compare 25). The bands were 161
relatively broad, indicating multiple positions with different arrangement to be occupied 162
by the Eu3+-cations. The heat treatment at 500°C, leads to longer lifetime for 163
luminescence resulting most probably from “burning out” of the OH-groups causing non-164
radiant transformation after excitation (see Fig. 3, TS1). 165
Heating normally also leads to improvement of both intensity and the line width 166
(narrowing) but had in this case the opposite effect: the 5D0-7F0 emission band used as 167
control is clearly broadened (from 1.4 to 2.8 nm for used spectral resolution of 0.3 nm) 168
and shifted to a shorter wavelength (Figures FS2, FS3). 169
170
[Fig 3] 171
172
Such transformation would be in agreement with the transfer of the cations to an even 173
larger number of sites with in general slightly improved symmetry. Thus we conclude 174
that the dopant is incorporated exclusively into the periphery of the TiO2 crystallites 175
(surface sites or the residual amorphous shell) and is transferred on heat-treatment into 176
better crystallized domains of, presumably, impurity phases like Eu2O3 or Eu2Ti2O7. The 177
intensity of luminescence is considerably decreased after heat-treatment also confirming 178
that the Eu cations are mostly not situated within the TiO2 lattice but in the parasite Eu-179
rich phases, where quenching of the radiant transition takes place. It is well known that 180
the cross- relaxation process between identical Eu3+ ions results in reducing the 181
5D1 emission with increasing Eu concentration. The narrowing of the emission spectra at 182
selected excitation wavelenghts for the heated sample (spectra not shown) as well as the 183
comparison of the 5D1-related emission and decays (Fig. 4) support for more 184
heterogeneous distribution of Eu3+ in the heated sample, including partial substitution of 185
Ti4+ by Eu3+ dopants and parasite Eu-rich phases (please, compare 25). 186
187
[Fig 4] 188
189
The obtained photoluminescence data reveal the formation mechanism for the produced 190
mesoporous anatase material, confirming the hypothesis presented in14: the anatase 191
particles are nucleating through a topotactic hydrolysis-polycondensation process rapidly 192
developing from the surface of the precursor alkoxide crystals inside them. The activity 193
of water attacking the faces of the crystal submerged into an aqueous medium is greatly 194
higher than that of the Eu3+-cations. No heterometallic species are formed on the 195
nucleation step and thus the primary oxometallate-type nuclei with anatase core 196
(MTSALs) 26,27 are simply free from europium dopant. The incorporation of the dopant 197
into the structure occurs later when Eu-cations start to diffuse into the amorphous shells 198
of the already formed primary particles. Thermal treatment initiates improved 199
crystallization and phase separation of the Eu-rich inter-particle domains and results in 200
the Eu-rich parasite phases with decreased intensity of luminescence as the result. The 201
same effect can be traced in the photoluminescence decay graphs (Figs.3a and 3b, the 202
decay times are provided in TS1). The graph corresponding to non-heat-treated samples 203
(Fig 3a) shows distinctly non-exponential decay, indicating low symmetry and, most 204
probably, multiplicity of the occupied sites. The one for the heat-treated sample (Fig.3b) 205
is more resembling an exponential decay due, supposedly, to improved symmetry of the 206
positions occupied by Eu3+ dopant cations. 207
An important feature that needs to be controlled to insure the possibility of long term 208
exploitation for a battery is the electrochemical performance of the electrode material. 209
The latter indicates potential capacity of the material to resist the loss of performance that 210
can be caused by coalescence of the grains and loss of the active surface in charge-211
discharge cycles. Special efforts have recently been directed at creation of thermally 212
stable TiO2-based electrode materials 28, and, in particular, the hydrothermal stability has 213
recently been a topic of intensive studies. 29 Energy transfer during charge-discharge 214
cycles can in time result in further sintering of the particles with considerable changes in 215
porosity and capacity as a result,5 – the effect much analogous to those of thermal 216
annealing. We have thus investigated the effects of thermal annealing on the crystal 217
structure, surface area and pore diameter in the material produced by rapid hydrothermal 218
synthesis (see Fig. 5). Heating to 500°C with speed of 10°C/min preserved the anatase 219
structure and was associated with the loss of active surface area from on average 250-300 220
m2/g to 110-120 m2/g (see TS2 and FS5) – still an impressive value typical for the best 221
analogs described in recent literature30-32. Heating to 800°C results not unexpectedly in 222
transition into the rutile phase and complete loss of active surface area (to about 2 m2/g) 223
because of sintering of the particles. 224
225
[Fig. 5] 226
227
The non-doped material obtained directly after rapid hydrothermal synthesis from solid 228
Ti(OMe)4 is practically fully crystalline, is completely free from organic impurities and 229
contains strongly aggregated anatase crystallites. Combination of these factors made it 230
potentially attractive as anode material for Li-ion batteries. It is worth noting that the 231
oxide matrix after synthesis contains up to 30 wt% adsorbed water and needs to be 232
dehydrated in vacuum in 6h at 120°C before lithium insertion. 233
The electrodes comprised of 85 wt% TiO2 nanoparticles, 8 wt% acetylene black, and 7 234
wt% polyvinylidene difluoride (PVDF) binder coated on copper foil. The electrochemical 235
properties of the prepared TiO2 anode were evaluated using coin-type cells (2032, 236
Hohsen) assembled in a helium-filled glove box. The Li/TiO2 half cells were cycled 237
between 1 and 2.5V at various current densities. The electrolyte was 1.2M LiPF6 in a 3:7 238
(by volume) mixture of ethylene carbonate and ethyl methyl carbonate. The reported 239
charge/discharge capacities are based on the active mass of TiO2 particles used in the 240
electrodes. 241
Fig. 6a displays the initial two discharge/charge curves of a Li/TiO2 half-cell, cycled 242
between 1 and 2.5 V at various current densities (22 mAg−1 to 112 mAg−1) and Fig 6b 243
shows corresponding capacity vs. cycle number plot. The first cycle discharge capacity 244
for the TiO2 particles is 299 mAh g−1 and the corresponding charging capacity is 225 245
mAh g−1 at a rate of C/15 (22mAg−1). A specific charge capacity of ~186 mAh g–1 was 246
obtained at C/10 rate; this value dropped to 177 and 167 mAh g–1 at C/6, and C/3, 247
respectively. Xu et al. hydrothermally synthesized anatase TiO2 nanotubes and reported 248
reversible capacity of 168 mAh g−1 at 210 mAg−1 current density with 98% coulombic 249
efficiency. 33 Wang et al. already demonstrated that aligned 1D-nanostructured materials 250
have a high surface to- volume ratio, meso–macroporous structure, and excellent activity 251
towards electrochemical lithium storage reactions. 34 The produced TiO2 electrode 252
demonstrated high capacity and stability, matching the best results for non-encapsulated 253
TiO2 reported in recent literature. 30 254
255
[Fig 6] 256
257
4. Conclusions 258
The results of this work permit to demonstrate that the proposed new rapid synthetic 259
approach, whose mechanism was confirmed here by photoluminescence studies, offers a 260
material with superior porosity and thermal stability, consisting of fully crystalline TiO2 261
grains even resistant to the thermal diffusion of Eu3+-cations. Particularly in view of the 262
simplicity of its preparation, it is highly interesting for preparation of anode materials for 263
Li-ion batteries. 264
265
Acknowledgements. The authors express their gratitude to the Swedish Research 266
Council (Vetenskapsrådet) for the Support to the grant “Molecular Precursors and 267
Molecular Models of Nanoporous Materials”. VGP and LA were supported by the Center 268
for Electrical Energy Storage: Tailored Interfaces, an Energy Frontier Research Center 269
funded by the US Department of Energy, Office of Science, Office of Basic Energy 270
Sciences. CT acknowledges the support from the Romanian National Authority for 271
Scientific Research (CNCS-UEFISCDI) (project number PN-II-ID-PCE-2011-3-0534). 272
273
Electronic supplementary includes the detailed information on the photoluminescence 274
(figures FS1-FS3, Table TS1) and thermal stability studies of the produced TiO2 material 275
(Table TS2 and figure FS4). This material is available free of charge via the Internet at 276
http://pubs.acs.org/ 277
References 278
279
(1) Arico, A.S.; Bruce, P.; Scrosati, B.; Tarascon, J.M.; van Schalkwijk, W. Nature 280
Mater., 2005, 4, 366. 281
(2) Goodenough, J.B., Park., K.S. J. Am. Chem. Soc., 2013, 135, 1167. 282
(3) Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Energy. Environ. Sci., 283
2011, 4, 3243. 284
(4) Marom, R.; Amalraj, S.F.; Leifer, N.; Jacob, D.; Aurbach, D. J. Mater. Chem., 285
2011, 21, 9938. 286
(5) Liu, H.; Bi, Z.H.; Sun, X.G.; Unocic, R.R.; Paranthaman, M.P., Dai, S.; Brown, 287
G.M. Adv. Mater., 2011, 23, 3450. 288
(6) Fröschl, T.; Hörmann, U.; Kubiak, P.; Kucerova, G.; Pfanzelt, M.; Weiss, C.K.; 289
Behm, R.J.; Hüsing, N.; Kaiser, U.; Landfesterd, K.; Wohlfahrt-Mehrens M. Chem. 290
Soc. Rev., 2012, 41, 5313. 291
(7) Wessel, C.; Zhao, L.A.; Urban, S.; Ostermann, R.; Djerdj, I.; Smarsly, B.M.; Chen, 292
L.Q.; Hu, Y.S.; Sallard, S. Chem. Eur. J., 2011, 17, 775. 293
(8) Armstrong, G.; Armstrong, A.R.; Canales, J.; Bruce, P.G. Chem. Commun., 2005, 294
2454. 295
(9) Armstrong, A.R.; Armstrong, G.; Canales, J.; Garcia, R.; Bruce, P.G. Adv. Mater., 296
2005, 17, 862. 297
(10) Beuvier, T.; Richard-Plouet, M. ; Mancini-Le Granvalet, M. ; Brousse, T. ; 298
Crosnier, O. ; Brohan, L. Inorg. Chem., 2010, 49, 8457. 299
(11) Ren, Y. ; Hardwick, L.J.; Bruce, P.G. Angew. Chem. Int. Ed., 2010, 49, 2570. 300
(12) Saravanan, K.; Ananthanarayanan, K.; Balaya, P. Energy Environ. Sci., 2010, 3, 301
939. 302
(13) Pol, V.G.; Kang, S.H.; Calderon-Moreno, J.M.; Johnson, C.S.; Thackeray, M.M. J. 303
Power Sources 2010, 195, 5039. 304
(14) Seisenbaeva, G.A.; Daniel, G.; Nedelec, J.M.; Gun’ko, Y.K.; Kessler, V.G. J. 305
Mater. Chem., 2012, 22, 20374. 306
(15) Kamat, P. J. Phys. Chem. C, 2012, 116, 11849. 307
(16) Yoon, S.; Manthiram, A. J. Phys. Chem. C, 2011, 115, 9410. 308
(17) Jung, H.G.; Yoon, C.S.; Prakash, J.; Sun, Y.K. J. Phys. Chem. C, 2009, 113, 309
21258. 310
(18) Zhang, X.; Kumar, P.S.; Aravindan, V.; Liu, H.H.; Sundaramurthy, J.; 311
Mhaisalkar, S.G.; Duong, H.M.; Ramakrishna, S.; Madhavi, S. J. Phys. Chem. 312
C, 2012, 116, 14780. 313
(19) Ryu, M.H.; Jung, K.N.; Shin, K.H.; Han, K.S.; Yoon, S. J. Phys. Chem. C, 2013, 314
117, 8092. 315
(20) Xiong, H.; Slater, M. D.; Balasubramanian, M.; Johnson, C. S.; Rajh, T. J. Phys. Chem. 316
Letters, 2011, 2, 2560. 317
(21) Qiu, J.X.; Zhang, P.; Ling, M.; Li, S.; Liu, P.R.; Zhao, H.J.; Zhang, S.Q. ACS Appl. 318
Mater. Interfaces, 2012, 4, 3636. 319
(22) Xin, X.; Zhou, X.F.; Wu, J.H.; Yao, X.Y.; Liu, Z.P. ACS Nano, 2012, 6, 11035. 320
(23) Zhao, B.; Shao, Z.P. J. Phys. Chem. C, 2012, 116, 17440. 321
(24) Luo, M.; Cheng, K.; Weng, W.J.; Song, C.L.; Du, P.Y.; Shen, G.; Xu, G.; Han, 322
G.R. Nanoscale Res. Lett., 2009, 4, 809. 323
(25) Li, J.G.; Wang, X.H.; Watanabe, K.; Ishigaki, T. J. Phys. Chem. B, 2006, 110, 324
1121-1127. 325
(26) Kessler, V.G.; Spijksma, G.I., Seisenbaeva, G.A.; Håkansson, S.; Blank, D.H.A.; 326
Bouwmeester, H.J.M. J. Sol-Gel Sci. Tech., 2006, 40, 163. 327
(27) Seisenbaeva, G.A., Kessler, V.G.; Pazik, R.; Strek, W. Dalton Trans, 2008, 3412. 328
(28) Ortiz, G.F.; Hanzu, I.; Djenizian, T.; Lavela, P.; Tirado, J.L.; Knauth, P. Chem. 329
Mater., 2009, 21, 63. 330
(29) Assaker, K.; Carteret, C.; Durand, P.; Aranda, L.; Stebe, M.J.; Blin, J.L. J. Phys. 331
Chem. C, 2013, in press DOI: 10.1021/jp405517w. 332
(30) Yang, M.C.; Leea, Y.Y.; Xu, B.; Powers, K.; Meng, Y.S. J. Power Sources, 2012, 333
207, 166. 334
(31) Yoon, S.; Manthiram, A. J. Phys. Chem. C, 2011, 115, 9410. 335
(32) Zhang, F.; Zhang, Y.; Song, S.Y.; Zhang, H. J. Power Sources, 2011, 196, 8618. 336
(33) Xu, J.W.; Jia, C.H.; Cao, B.; Zhang W.F. Electrochim. Acta, 2007, 52, 8044. 337
(34) Wang, D.W.; Fang, H.T.; Li, F.; Chen, Z.G.; Zhong, Q.S.; Lu, G.Q.; Cheng H.M. 338
Adv. Funct. Mater., 2008, 18, 3787. 339
340
341
342
Figure legends 343
344
Fig. 1. SEM and TEM views of the rod-shaped anatase microparticles produced by rapid 345
hydrothermal synthesis from rod-shaped Ti(OMe)4 microcrystals. 346
347
Fig. 2. Luminescence spectra for non-heat-treated sample (TE) and the sample heat-348
treated at 500°C for 1 h (TE-500) in the full spectral range (a) and specifically for the 349
5D0-7F0 transition (b). 350
351
Fig. 3 Luminescence lifetimes for non-heat-treated sample (TE) and the sample heat-352
treated at 500°C for 1 h (TE-500) – (a) and (b) respectively. The legend format is 353
λ(excitation)/λ(emission). 354
355
Fig. 4 Comparion between 5D1- related emission spectra and decays of Eu- TiO2 before 356
and after thermal treatment at 500 °C (λex / λem = 464.8 nm / 536 nm). 357
358
Fig. 5 Nitrogen sorption isotherms for the dehydrated material after synthesis (a), the 359
material heat treated in dynamic regime up to 500°C (b) and the material heat-treated at 360
800°C. 361
362
Fig. 6. Cycle performance of the TiO2-based anode material. 363
Figure 5 375
0.0 0.2 0.4 0.6 0.8 1.00
2
4
6
8
10
12
14
16a
b
Volu
me
sorb
ed (c
m3 .g
-1)
relative pressure p/p0
c
376
Top Related