Chem. Mater.

2010, 22, 1173–1179 1173

DOI:10.1021/cm902613h

Tailored Preparation Methods of TiO2 Anatase, Rutile, Brookite:

Mechanism of Formation and Electrochemical Properties†
Damien Dambournet,* Ilias Belharouak,* and Khalil Amine
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue,
Argonne, Illinois 60439
Received August 24, 2009. Revised Manuscript Received November 3, 2009

Using a simple aqueous precipitation method based on a low-cost titanium oxysulfate precursor,
we have prepared three TiO2 polymorphs: anatase, rutile, and brookite. Although the anatase form
can be directly obtained from the thermolysis reaction of an oxysulfate solution, the rutile and the
brookite have been prepared by the addition of oxalate species. Depending on the concentration, the
oxalate anions have been shown to act either as a ligand with the stabilization of a titanium oxalate
hydrate, Ti2O3(H2O)2(C2O4) 3 H2O, or as a chelating agent with the isolation of the rutile phase. The
brookite form was obtained by thermal decomposition of the oxalate hydrate at a temperature as low
as 300 °C. The resulting solid consisted of nanodomains of TiO2 brookite embedded in large
micrometer-size particles and exhibited a high specific surface area of 255 m2/g because of the
mesoporosity arising from the removal of water from the oxalate species. This type of morphology is
of interest for lithium-ion batteries because of an easier coating process and a higher surface contact
between the material and the electrolyte that enhanced the electrochemical activity. Finally, based on
electrochemical characterizations, TiO2 brookite provided higher volumetric energy density than
comparable nanomaterials.

1. Introduction achieved by the TiO2 anode is much lower than the

theoretical one (335 mA h/g) based on the full electro-
Beyond their wide use in small electronic devices,
chemical activation of the Ti4þ/Ti3þ redox couple and still
lithium-ion batteries are now facing the challenge of
needs to be sustained over long-term cycling. This capa-
meeting the energy and power requirements for plug-in
city stability can be achieved by the use of nanostructured
hybrid vehicles and electric vehicles. Research has been
titania materials. Indeed, nanomaterials have attracted
focused on the development of new electrode materials
significant attention in the energy storage and conversion
that could provide higher power, longer cycle life, lower
field owing to their specific features2 that enhance the
cost, and enhanced safety. With regard to the negative
electrochemical activity so that full lithium ion reversi-
electrode, the mechanism of lithiation of carbonaceous
bility can be achieved. Nevertheless, in addition to low
materials is governed by the formation of a solid-electro-
volumetric energy density, the need for the large-scale
lyte interface (SEI) layer generated after reduction of the
production of nanomaterials can be argued to be disad-
electrolyte species. This SEI layer enables the reversibility
vantageous for Li-ion batteries, because their preparation
of lithium-ion insertion, leading to a high energy density.
can be very complex2 and can add tremendously to the
However, it is thermally unstable and therefore poses
cost of the final battery pack.
safety concerns. These concerns are allayed by operating
Since the 1970s, the so-called “chimie douce” has
at a higher voltage than that of metallic lithium, which
introduced synthetic methods that lead to new materials
prevents the decomposition of the electrolyte. Titanium
with unique features, including the synthesis of hybrid
oxide (titania) is an interesting alternative anode1 to
materials or the low temperature synthesis of oxides.3 The
graphite because of its operating voltage (∼1.5 V), which
precipitation process in aqueous solutions is one of the
may enable extended cycle life as well as enhanced safety.
synthetic methods developed through the “chimie
Additionally, titanium is abundant, nontoxic, and inex-
douce.” This process has been used to prepare titanium
pensive. These characteristics are of great importance
oxide compounds with easy control of the size/morphol-
with regard to the production of batteries in large scale.
ogy as well as the structural arrangement.4 The latter
However, the practical capacity (∼170-200 mA h/g)
advantage is relevant since titanium dioxide has several
allotropic forms with different structures. The most
†
Accepted as part of the 2010 “Materials Chemistry of Energy Conversion
Special Issue”. (2) Arico, A. S.; Bruce, P. G.; Scrosati, B.; Tarascon, J.-M.; Schalkwijk,
*Corresponding author. E-mail: dambournet@[Link] (D.D.); belharouak@ W. V. Nat. Mater. 2005, 4, 366.
[Link] (I.B.). (3) Livage, J. New J. Chem. 2001, 25, 1.
(1) Deng, Da; Kim, Min Gyu; Lee, Jim Yang; Cho, Jaephil Energy (4) Jolivet, J. P.; Cassaignon, S.; Chaneac, C.; Chiche, D.; Tronc, E.
Environ. Sci. 2009, 2, 818. J. Sol-Gel Sci. Technol. 2008, 46, 299.

r 2009 American Chemical Society Published on Web 11/18/2009 [Link]/cm

1174 Chem. Mater., Vol. 22, No. 3, 2010 Dambournet et al.

well-known are rutile (tetragonal, P42/mnm), anatase

(tetragonal, I41/amd), and brookite (orthorhombic,
Pbca).5 Their structures are all built upon the connection
of TiO6 octahedra. Although the anatase structure con-
sists of edge-sharing TiO6 octahedra, the rutile and the
brookite frameworks exhibit both corner- and edge-
sharing configurations (Figure 1). These phases can be
prepared in an aqueous medium.6 Nevertheless, because
of the metastability of the brookite form, its preparation
appears to be more challenging. To the best of our Figure 1. Representations of the TiO2 anatase, rutile, and brookite forms.
knowledge, only two methods have been reported on
scanning calorimetry (DSC) analysis was conducted with a
the aqueous precipitation of pure TiO2 brookite. Potier
Perkin-Elmer Pyris-1 instrument. The DSC curves were re-
et al.7 prepared it by the thermolysis reaction of TiCl4 in
corded between room temperature and 400 °C at a scan rate
concentrated HCl, followed by peptization with concen- of 5 °C/min. An empty stainless-steel capsule was used as a
trated nitric acid. The other method is the oxidation of reference pan.
TiCl3 in an aqueous solution containing urea.8 Because of Nitrogen adsorption isotherms were recorded at 77 K on a
the difficulty in preparing this TiO2 polymorph, only a NOVA 2200e instrument. The powder sample (∼200 mg) was
few studies9-12 have been devoted to its use as an anode evacuated at 200 °C for 2 h prior to N2 adsorption. The total
for lithium ion-batteries, as opposed to the anatase and pore volume was calculated from the volume of nitrogen
rutile phases, which have been extensively studied. adsorbed at relative pressure of P/P0 = 0.986. The specific
In this paper, we report on isolating the three above- surface area was calculated from the BET method applied in the
mentioned TiO2 polymorphs by using the chimie douce P/P0 range between 0.04 and 0.29. The pore size distribution was
obtained by means of the Barrett-Joyner-Halenda algorithm
tools. A mechanism for their formation is proposed, and
using the adsorption branch.
their electrochemical activity is characterized.
Electrochemical measurements were carried out with
CR2032-type coin cells. The negative electrodes were made of
2. Experimental Procedure 80 wt % active oxide materials, 10 wt % acetylene black as the
The synthesis process consisted of the thermolysis of titanium conductive agent, and 10 wt % polyvinylidene difluoride binder.
oxysulfate (Sigma Aldrich, Supelco) in an aqueous solution with The electrolyte was 1.2 M LiPF6 dissolved in a (3:7 volume ratio)
a concentration of 0.9 M. First, TiOSO4 is dissolved in water by mixture of ethylene carbonate and ethyl methyl carbonate. The
slight heating. The precipitation of TiO2 is then performed by cells were assembled with lithium metal as the negative electrode
heating the solution at 90 °C for 4 h. The powder is recovered by and were tested in the voltage range of 1-3 V.
centrifugation (4000 rpm) or filtration, and then washed with
water. To ensure the TiO2 stoichiometry, we performed thermo- 3. Results and Discussion
gravimetric analysis to define an appropriate post-treatment
annealing. In a second step of this investigation, this synthesis 3.1. Synthesis and Structural Characteriza-
was performed in the presence of different anionic species tions. 3.1.1. Thermolysis of an Aqueous Oxysulfate So-
through the use of lithium salt additives, i.e., LiNO3, LiCl, lution. Most TiO2 synthesis has involved the use of
Li2SO4, and Li2C2O4 (Sigma Aldrich). To do so, we dissolved titanium chloride or alkoxide precursor. In the present
the lithium and titanium salts simultaneously. paper, we used a titanium oxysulfate-sulfuric acid com-
The prepared samples were analyzed by various methods. plex hydrate (TiOSO4 3 H2O 3 H2SO4) as a precursor,
Powder X-ray diffraction analysis was performed with a Sie- which is a low cost salt and, as opposed to other titanium
mens D5000 diffractometer (Cu KR). The samples were scanned salts, is easy to handle. As a starting point, the thermolysis
from 2θ = 10-80° at a scan rate of 5 s per 0.02°. Scanning reaction of an aqueous titanium oxysulfate solution was
electron microscopy (SEM, Hitachi S-4700-II) was performed at
studied without anionic species additives. The presence of
the Electron Microscopy Center at Argonne National Labora-
sulfuric acid in the starting precursor induced a strong
tory. Thermogravimetric analysis (TGA) was performed with a
Seiko Exstar 6000 instrument at a scan rate of 5 °C/min in the acidic medium with a pH value of 0.1. TiO2 was precipi-
temperature range of room temperature to 800 °C. Differential tated at 90 °C after 4 h of reaction. The resulting powder
exhibits agglomerates of nanosize particles whose X-ray
(5) Inorganic Crystal Structure Database, version 2009-1; Fachinforma-
diffraction pattern is that of TiO2 anatase (Figure 2). This
tionszentrum Karlsruhe: Karlsruhe, Germany, 2009. result suggests that sulfate species act as a directing agent
(6) Jolivet J Sol-Gel Sci. Technol. 2008, 46, 299. that favors the formation of anatase at the expense of the
(7) Potier, A.; Chaneac, C.; Tronc, E.; Mazerolles, L.; Jolivet, J. P.
J. Mater. Chem. 2001, 11, 1116. thermodynamically stable phase, i.e., the rutile form. In
(8) Li, J.-G.; Tang, C.; Li, Di; Haneda, H.; Ishigaki, T. J. Am. Ceram. general, in an aqueous medium, titanium cations are
Soc. 2004, 87(7), 1358–1361.
(9) Anji Reddy, M.; Satya Kishore, M.; Pralong, V.; Varadaraju, U. solvated and form 6-fold-coordinated, charged com-
V.; Raveau, B. Electrochem. Solid-State Lett. 2007, 10(2), A29– plexes [TiL6]zþ in which the nature of the ligand L is
A31.
(10) Anji Reddy, M.; Pralong, V.; Varadaraju, U. V.; Raveau, B. dictated by the pH of the solution and the presence of
Electrochem. Solid-State Lett. 2008, 11(8), A132–A134. species that can act as complexing agents.13 In the absence
(11) Lee, D. H.; Park, J. G.; Choi, K. J.; Choi, H. J.; Kim, D. W. Eur. J.
Inorg. Chem. 2008, 878.
(12) Lee, D.-H.; Park, J.-G.; Choi, K. J.; Choi, H.-J.; Kim, D.-W. Cryst. (13) Jolivet, J. P. Metal Oxide Chemistry and Synthesis: From Solution
Growth Des. 2008, 8, 12. to Solid State; Wiley: New York, 2000.
Article Chem. Mater., Vol. 22, No. 3, 2010 1175

Figure 2. X-ray diffraction powder pattern of TiO2 anatase obtained

from the thermolysis of an oxysulfate solution. Inset: Scanning electron Figure 3. X-ray diffraction powder pattern of the TiO2 anatase obtained
microscopy image of the solid. from the thermolysis of an oxysulfate solution with and without the
addition of different anionic species.
of complexing ligand, acidity plays a major role. For
instance, in high acidic medium, because of the polariza-
bility of Ti4þ ions, the complex [Ti(H2O)6]4þ undergoes a
spontaneous hydroxylation reaction, forming the
[Ti(OH)(H2O)5]3þ complex. Further hydroxylation reac-
tions lead to the formation of a zero-charge complex with
the following formula: [Ti(OH)4(H2O)2]0. These reactions
can be promoted by either adding a base (coprecipitation
process) or heating the solution (thermolysis process). By
condensation reactions, this complex can result in the
formation of a solid phase through the creation and
growth of the nuclei. This process is based on olation
and oxalation reactions. In the presence of complexing
agents that can react with the coordination sphere of the
cation, the solid phase is likely to form from different
zero-charge precursors, leading to the stabilization of one Figure 4. X-ray diffraction powder pattern as a function of the R =
[C2O42-]/[Ti4þ] molar ratio (* sample holder).
particular phase. In our case, sulfate species play the role
of the complexing agents and can enter the coordination moting role. In contrast, the addition of the chloride
sphere of Ti4þ ions. Koelsh et al.,14 indeed, proposed the anion, a strong complexing agent, led to a poorly crystal-
existence of the following zero-charge precursor: lized anatase phase (Figure 3). Chloride anions can enter
[Ti(OH)2SO4(H2O)2]0, where SO42- ions act as bidentate the first coordination sphere of titanium, forming hydro-
ligands. More recently, the speciation of titanium(IV) in xochloro complexes. As opposed to sulfate species, the
sulfuric acid solutions has shown the occurrence of chloride anion favors the formation of the brookite phase
1Ti:1SO4 and 1Ti:2SO4 species, with the predominance after formation of the suggested zero-charge precursor
of the 1:1 complex.15 These complexes exist in low [Ti(OH)2Cl2(H2O)2]0.7 Finally, in the case of nitrate
amounts, suggesting their role as a catalyst or structure- NO3-, which is a weak complexing anion, the prepared
directing agent favoring the anatase type structure. sample presents a slight decrease in the anatase crystal-
According to Jolivet,13 the formation of sulfate species linity (Figure 3).
in the vicinity of the cation may favor the condensation 3.1.2. Addition of Oxalate Species. The oxalate anion
of opposed coplanar edges, leading to the anatase C2O42- has been considered for its properties as a rigid
configuration. bidentate ligand that can link two metallic centers, but
To further probe the effect of additional species in also for its chelating properties.16 To probe the reactivity
solution, experiments were performed with anionic spe- of the oxalate anion with titanium ions, the R =
cies having different complexing strength: SO42-, NO3-, [C2O42-]/[Ti4+]molar ratio has been tuned. Figure 4
and Cl-. The molar ratio between Ti4þ and the additional shows the evolution of the powder X-ray diffraction
anionic species was fixed at one. X-ray diffraction analy- patterns as a function of the [C2O42-] content. Three
sis, shown in Figure 3, was used to probe the effect of domains were distinguished. A low concentration (R =
these species. The sulfate species improved the crystal- 0.2) yielded a phase mixture consisting of anatase (major
linity of the prepared phase, which confirmed their pro- phase) and rutile. For R = 1, the titanium oxalate-based
compound Ti2O3(H2O)2(C2O4) 3 H2O was identified.
(14) Koelsh, M.; Cassaignon, S.; Jolivet, J. P. Mater. Res. Soc. Symp.
Proc. 2004, 822, 73.
(15) Szilagyi, I.; Konigsberger, E.; May, P. M. Inorg. Chem. 2009, 48, (16) Rao, C. N. R.; Natarajan, S.; Vaidhyanathan, R. Angew. Chem.,
2200. Int. Ed. 2004, 43, 1466.
1176 Chem. Mater., Vol. 22, No. 3, 2010 Dambournet et al.

Ti2O3(H2O)2(C2O4) 3 H2O has been subjected to differ-

ent thermal treatment and the corresponding X-ray dif-
fraction pattern is shown in Figure 7. Surprisingly, the
titanium oxalate hydrate phase decomposed into the
metastable TiO2 brookite form. Note that because the
main diffraction line of the anatase form is close to the
one for the brookite form, the thermal decomposition of
the Ti2O3(H2O)2(C2O4) 3 H2O had been previously re-
ported to lead to the TiO2 anatase form.17 At a tempera-
ture as low as 300 °C, the X-ray pattern of the brookite
Figure 5. Scanning electron microscopy image of [Ti2O3(H2O)2]- was clearly identified. The broadness of the X-ray lines
(C2O4) 3 H2O. indicates the formation of nanosized brookite. An in-
crease in the temperature led to an improvement of the
Finally, the higher oxalate content (R = 2) yielded an
crystallinity. At 600 °C, the brookite form started to
oxide having the rutile-type structure. Depending on the
decompose, with the detection of a tiny peak ascribed to
concentration, the oxalate anion can either act as a ligand
the main diffraction peak of the rutile phase (Figure 7).
with the stabilization of an oxalate hydrate phase Ti2O3-
In a previous study by Tomita et al.,18 TiO2 brookite
(H2O)2(C2O4) 3 H2O (R = 1) or as a chelating agent (R =
was also reported to be formed using an organic-
2) with the stabilization of the rutile phase with a low
inorganic compound, (NH4)6[Ti4(C2H2O3)4(C2H3O3)2-
yield. At first, it was surprising that the increase of the
(O2)4O2]. Nevertheless, this water-soluble titanium com-
oxalate concentration (R = 2) did not favor the forma-
plex has to be treated under hydrothermal conditions to
tion of the oxalate hydrate Ti2O3(H2O)2(C2O4) 3 H2O, but
form TiO2 brookite. The facile synthesis and low stability
led to the stabilization of an oxide. However, because of
of Ti2O3(H2O)2(C2O4) 3 H2O make it a suitable precursor
the chelating properties of C2O42- anions, further com-
as part of a simple preparation method for TiO2 brookite.
plexation of titanium ions by the oxalate ligands inhibits
An additional salient point about this preparation meth-
the stabilization of Ti2O3(H2O)2(C2O4) 3 H2O and instead
od is the preservation of the morphology upon annealing
favors the formation of the thermodynamically stable
(Figure 8). As evident from the SEM images, the eggshell
TiO2 rutile. The blocking effect of the oxalate anions on
morphology is retained despite the creation of porosities
condensation reaction was also confirmed by the low
arising from the removal of water and oxalate species.
yield from the reaction, i.e., 30%, which can be enhanced
This observation has been confirmed by N2 adsorption
by an increase of the synthesis temperature.
(Figure 9). The curve in Figure 9 is typical of a type IV
Figure 5 shows a scanning electron micrograph of the
isotherm,19 which is consistent with mesoporous TiO2
Ti2O3(H2O)2(C2O4) 3 H2O compound. This solid con-
brookite. The surface area calculated by the BET method
sists of 3 μm particles having an eggshell morphology.
was 255 m2/g, which can only be explained by the
The structure and composition of this phase have been
existence of significant porosity created at the level of
recently reinvestigated by Boudaren et al.17 The phase
the eggshell micrometer-size particles. The mesopore size
consists of TiO6-based layers that are interconnected by
was centered at 3.4 nm, and the total porous volume was
oxalate anions, and it crystallizes in an orthorhombic
0.25 mL/g. Finally, based on the high surface area and
symmetry (Cmca). Profile matching (Le Bail method)
porosity numbers associated with the broadness of the
confirmed the phase purity. The unit cell parameters are
diffraction lines, TiO2 brookite obtained after decompo-
in agreement with the literature, i.e., a = 15.436(3) Å, b =
sition of the titanium oxalate hydrate consists of nano-
10.421(2) Å, and c = 9.692(2) Å. The chemical composi-
domains embedded in micrometer-size particles.
tion was confirmed by thermogravimetric analysis
3.2. Electrochemical Characterization. Figure 10 pre-
(Figure 6, left), which indicated a total weight loss of
sents the discharge and charge profiles of the three TiO2
43.7% (against 44.1% theoretically). The different steps
forms cycled between 1 and 3 V (vs Li0) at a C/25 rate. A
of the thermal decomposition are related to the dehydra-
“1C” rate here refers to the application of 335 mA/g
tion (below 200 °C) and removal of the oxalate species
current density in a cell. The lithium insertion occurs
(above 200 °C). The removal of oxalate species occurs in
typically at around 1.4-1.7 V according to the following
two steps: the formation of a carbonate phase at around
scheme: xLiþ þ TiO2 þ xe- T LixTiO2. Such a reaction
350 °C and the decomposition of the oxalate to form
implies the reduction of Ti4þ into Ti3þ ions.20 The inser-
TiO2.17 Differential scanning calorimetric analysis was
tion of one Liþ ion per unit formula is equivalent to the
also conducted on Ti2O3(H2O)2(C2O4) 3 H2O (Figure 6,
achievement of the 335 mA h/g theoretical capacity of
right). Two endothermic peaks were detected: a strong
TiO2. During the initial discharge, all three phases
peak occurring at 275 °C and a weak one at 295 °C. Both
peaks are related to the removal of the oxalate species. No
exothermic event related to the crystallization of TiO2 has (18) Tomita, K.; Petrykin, V.; Kobayashi, M.; Shiro, M.; Yoshimura,
been detected. M.; Kakihana, M. Angew. Chem., Int. Ed. 2006, 45, 2378.
(19) Brunauer, S.; Emmett, P. H.; Teller, E. J. Am. Chem. Soc. 1938
60(2), 309.
(17) Boudaren, C.; Bataille, T.; Auffr
edic, J. P.; Lou€er, D. Solid State (20) Sodergren, S.; Siegbahn, H.; Rensmo, H.; Lindstom, H.; Hagfeldt,
Sci. 2003, 5, 175. A.; Lindquist, S. E. J. Phys. Chem., B 1997, 101, 3087.
Article Chem. Mater., Vol. 22, No. 3, 2010 1177

Figure 6. Thermogravimetric (left) and differential scanning calorimetric (right) analyses of [Ti2O3(H2O)2](C2O4) 3 H2O.

Figure 7. X-ray diffraction analysis of [Ti2O3(H2O)2](C2O4) 3 H2O ther-

mally treated at different temperatures for 4 h under air.

showed capacities close to the theoretical one, i.e., 333

mA h/g (0.99Liþ) for the rutile, 310 mA h/g (0.92Liþ) for Figure 8. Scanning electron microscopy images of [Ti2O3(H2O)2]-
(C2O4) 3 H2O (top image) and TiO2 brookite (bottom) obtained by thermal
the anatase, and 282 mA h/g (0.84Liþ) for the brookite. decomposition at 300 °C.
During the charge (deinsertion), the observed irreversible
capacities (31% for anatase, 26% for rutile, and 21% for
brookite) are indicative of the lithium ion remaining
(0.28 Liþ for anatase, 0.26 Liþ for rutile, 0.18 Liþ for
brookite) in the pristine structures. Note that despite the
generation of slightly lower capacity, the Coulombic
efficiency was higher in the case of TiO2 brookite.
In general, the lithium insertion in electrode materials can
occur in a homogeneous or heterogeneous manner, leading
to different structural behavior upon lithiation. Lithium
insertion can indeed proceed via single-phase solid-solution
behavior or two-phase structural transition. The voltage
profile (Figure 10) accounts for the structural behavior
upon lithiation. During the first discharge, the brookite Figure 9. N2 adsorption isotherms of TiO2 brookite prepared by thermal
exhibits a smooth curve, indicating a solid-solution beha- decomposition of Ti2O3(H2O)2(C2O4) 3 H2O at 300 °C.
vior. On the contrary, both anatase and rutile display a
ascribed to a structural rearrangement upon lithiation,
much more complex discharge profile, with the existence of
from the original rutile P42/mnm to its lithiated form P2/
plateau zones that likely account for the coexistence of
m at 1.4 V and finally to a layered structure at 1.1 V.21 The
biphasic domains. For the rutile form, except the first
last plateau leads to a drastic and irreversible structural
discharge, further charge/discharge processes indicate sin-
gle-phase reversible behavior. For the first discharge, two (21) Borghols, W. J.; Wagemaker, M.; Lafont, U.; Kelder, E.; Mulder,
plateau zones are observed, at 1.4 and 1.1 V, which were F. M. Chem. Mater. 2008, 20, 2949.
1178 Chem. Mater., Vol. 22, No. 3, 2010 Dambournet et al.

Figure 10. Voltage profile of the different TiO2 forms cycled at C/25.

change, which explains the single-phase insertion/extrac-

tion profile after the first discharge. This behavior has only
been observed for nanosized rutile.22 As for the anatase,
bulk crystallites display a two-phase transition profile
characterized by a flat plateau zone related to the coexi-
stence of a Li-poor phase, Li0.05TiO2, having the anatase
original space group, i.e., I41/amd, and a Li-rich
phase Li0.5TiO2 (Imma).23 For nanosized particles, in
addition to the Li-rich phase, the anatase type structure
can behave as a solid solution with the insertion of up to
1 Liþ ion per TiO2.24 The brookite was found to present a
partial amorphization upon lithiation,9 so that it was
difficult to probe structural changes. Nevertheless, upon
lithium removal, the phase can recover its initial crystal-
linity in agreement with single-phase behavior. Research is
underway to fully elucidate the structural behavior of the
brookite upon lithiation.
Because of its originality in term of morphology,
further electrochemical characterizations have been per-
formed on the TiO2 brookite form (Figure 11). This type
of morphology is indeed of interest for lithium-ion
batteries for several reasons. First, in terms of electrode
fabrication, spherical-type particles exhibit a better
dispersibility suitable during the coating process of the
material on the current collector. Second, the mesopo-
rosity provides a higher surface contact between the
material and the electrolyte, which enhances the electro-
chemical activity.25 Finally, this type of morphology can Figure 11. (a) Gravimetric and volumetric capacity of TiO2 brookite
under C/10 (33.5 mA/g); (b) rate capability of TiO2 brookite.
provide high volumetric energy density in a battery. For
instance, most nanomaterials dedicated to Li-ion volumetric capacity has been calculated from the pro-
battery applications suffer from low packing density, duct of the gravimetric capacity and tap density. TiO2
which despite the enhancement of their electrochemical brookite showed a stable cycling behavior with the
performances compromises the overall energy density of retention of 155 mA h/g after 20 cycles. Such a value is
the battery. In our case, the titanium oxalate hydrate in the range of those found for nanosize brookite.10 The
provides a tap density of 1.2 g/cm3, which slightly volumetric capacity was around 165 mA h/cm3, which is
decreases upon annealing, to 1.05 g/cm3. The cyclability significantly higher than most nanosized TiO2 materials
of TiO2 brookite performed under a C/15 rate is pre- because the latter display lower packing density,
sented in Figure 11. Both gravimetric (mA h/g) and i.e., 0.5-0.8 g/cm3.
volumetric (mA h/cm3) capacities are reported. The The evolution of the capacity of TiO2 brookite with
increasing rates has been also studied and is displayed in
(22) Hu, Y.-S.; Kienle, L.; Guo, Y.-G.; Maier, J. Adv. Mater. 2006, 18, Figure 11. TiO2 brookite exhibited a specific discharge
1421. capacity of 170 mA h/g under C/10 rate which reduced to
(23) Wagemaker, M.; Kearley, G. J.; van Well, A. A.; Mutka, H.;
Mulder, F. M. J. Am. Chem. Soc. 2003, 125, 840. 152, 113, and 55 mA h/g at C/5, 1C and 5C rates,
(24) Wagemaker, M.; Borghols, W. J. H.; Mulder, F. M. J. Am. Chem. respectively. Such a decrease of capacity while increasing
Soc. 2007, 129, 4323.
(25) Guo, Y. G.; Hu, Y. S.; Maier, J. Chem. Commun. 2006, 2783. the current density can be ascribed to the insulating
Article Chem. Mater., Vol. 22, No. 3, 2010 1179

character of TiO2. There are, however, several ways to investigation of the thermal behavior of the Ti2O3(H2O)2-
improve the electronic conductivity of insulating materi- (C2O4) 3 H2O has shown that it decomposes into the TiO2
als including the use of conductive additives such as brookite form at a temperature as low as 300 °C. The
glassylike phases,26 carbon27 or metal28 coating, or design resulting solid consisted of nanodomains of TiO2 broo-
of hierarchical network.29 Future works are thus under- kite embedded in large micrometer-size mesoporous par-
way to improve the rate capability of TiO2 brookite and ticles and exhibited a very high specific surface area of 255
will be reported elsewhere. m2/g because of the mesoporosity. The electrochemical
properties of the three phases were characterized in a
4. Conclusion lithium cell configuration. The cell tests showed that all
phases approached the theoretical capacity (335 mA h/g) of
The investigation of the thermolysis reaction of a
one lithium ion insertion in TiO2 for the first discharge.
titanium oxysulfate with and without the presence of
Except for certain differences in voltage profiles that are
additives has been shown to be very rich through the
due to the basic differences in the lithium insertion mechan-
preparation of three different forms of TiO2, which are
ism among the three structural frameworks, the operating
the anatase, rutile, and brookite. Because of its ability to
voltage of the anatase, rutile, and brookite phases is about
react with the coordination shell of the Ti4þ ions, the
1.7 V, with most of the capacity being achieved above 1 V.
promoting effect of sulfate (SO42-) species toward the
Within this voltage region, most electrolytes are electro-
anatase form has been confirmed. The supplemental
chemically very stable, and combining these lithium inser-
addition of anionic species such as NO3- or Cl- led to
tion materials with higher potential materials, such as
the anatase form exhibiting different crystallinity depend-
LiMn2O4 or LiNi0.5Mn1.5O4, would result in battery sys-
ing on the ability of the anion to react with Ti4þ ions in
tems with better life and safety. Moreover, this work has
solution. For instance, for a chloride anion having a
shed light on the electrochemical properties of the TiO2
strong complexing strength, the prepared solid consisted
brookite phase; such data are scarce in the literature. Our
of an ill-crystalline anatase phase. Further investigating
experimental procedure has established a new facile meth-
the use of additives for the preparation of TiO2, oxalate
od to prepare the metastable brookite phase. The high
species (C2O42-) have been considered because of its
packing density particles built from nanosize crystallites
strong complexing properties. Increasing the R =
associated with a high surface area because of the porosity
[C2O42-]/[Ti4þ] molar ratio led to the successive isolation
makes this morphology, unique and suitable for a large
of the titanium oxalate hydrate Ti2O3(H2O)2(C2O4) 3 H2O
scale production and its use as electrode material. Even
(R = 1) and the rutile phase (R = 2). The isolation of the
with slightly lower capacity compared to anatase or rutile,
TiO2 rutile using high concentration of oxalate empha-
brookite’s high volumetric capacity is of great importance if
sized the chelating properties of this anion. A detailed
the phase is to be used in full-scale batteries.
(26) Zhou, H. S.; Li, D. L.; Hibino, M; Honma, I. Angew. Chem., Int.
Ed. 2005, 44, 797.
(27) Fu, L. J.; Liu, H.; Zhang, H. P.; Li, C.; Zhang, T.; Wu, J. P.; Holze, Acknowledgment. This research was funded by the U.S.
R.; Wu, H. Q. Electrochem. Commun. 2006, 8, 1. Department of Energy, FreedomCAR and Vehicle Techno-
(28) Mancinia, M.; Kubiaka, P.; Geserickc, J.; Marassi, R.; H€ usingc, logies Office. Argonne National Laboratory is operated for
N.; Wohlfahrt-Mehrensa, M. J. Power Sources 2009, 189, 585.
(29) Guo, Y.-G.; Hu, Y.-S.; Sigle, W.; Maier, J. Adv. Mater. 2007, 19, the U.S. Department of Energy by UChicago Argonne,
2087. LLC, under Contract DE-ACO2-06CH11357.