Nanometric anatase lattice stabilised by cation vacancies, methods for the production thereof, and uses of same

Abstract

The present application describes a process for the preparation of titanium-based compounds having an anatase type structure with cationic vacancies arising from a partial substitution of oxygen atoms by fluorine atoms and hydroxyl groups. Electrochemically active materials comprising the titanium-based compounds for use in lithium-ion battery electrodes are also described.

Claims

1. A titanium-based compound of the general chemical formula:
Ti.sub.1-x-y.sub.x+yF.sub.4x(OH).sub.4yO.sub.2-4(x+y) wherein, represents a cationic vacancy; and x and y are numbers such that 0.01(x+y)<0.5, wherein x and y are not zero, and wherein the titanium-based compound has an anatase type structure.

2. The titanium-based compound according to claim 1, wherein x and y are numbers such that 0.04(x+y)<0.5.

3. The titanium-based compound according to claim 1, which is Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12.

4. An electrochemically active material comprising the titanium-based compound of claim 1.

5. An electrode comprising the electrochemically active material of claim 4 on a current collector.

6. A lithium-ion battery comprising the electrode of claim 5, a counter-electrode and an electrolyte between the electrode and the counter-electrode.

7. A method for preparing a titanium-based compound having an anatase type structure with cationic vacancies arising from a partial substitution of oxygen atoms by fluorine atoms and hydroxyl groups, comprising the steps of: a) preparing a solution containing a titanium precursor, a fluorinating agent and a solvent; and b) precipitating a titanium-based compound having the general chemical formula Ti.sub.1-x-y.sub.x+yF.sub.4x(OH).sub.4yO.sub.2-4(x+y), wherein represents a cationic vacancy, wherein x and y are numbers such that 0.01(x+y)<0.5, and wherein x and y are not zero.

8. The method according to claim 7, wherein the titanium precursor is selected from titanium C.sub.2-C.sub.10alkoxides and titanium chloride.

9. The method according to claim 7, wherein the fluorinating agent is an agent which provides fluoride anions.

10. The method according to claim 7, wherein the solvent of the solution of step (a) comprises an organic solvent or a mixture of an organic solvent and water.

11. The method according to claim 10, wherein the organic solvent is selected from C.sub.1-C.sub.10alcohols, dialkylketones, ethers, esters or a combination thereof.

12. The method according to claim 10, wherein the organic solvent is methanol, ethanol, isopropanol, butanol, octanol or a combination thereof.

13. The method according to claim 7, wherein step (a) or (b) further comprises a thermal treatment.

14. The method according to claim 13, wherein the thermal treatment comprises heating the solution of step (a) at a temperature within the range of from about 50 C. to about 220 C.

15. The method of claim 13, wherein a degree of cationic vacancies is controlled by adjusting the temperature of the thermal treatment.

16. The method according to claim 11, wherein the dialkylketones are acetone.

17. The method of claim 7, wherein x and y are numbers such that 0.04(x+y)<0.5.

18. A titanium-based compound prepared by the process method according to claim 7, wherein said compound is of the general chemical formula:
Ti.sub.1-x-y.sub.x+yF.sub.4x(OH).sub.4yO.sub.2-4(x+y) wherein, represents a cationic vacancy; and x and y are numbers such that 0.01(x+y)<0.5, and wherein x and y are not zero.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows an x-ray powder diffraction pattern of a phase prepared according to example 1. The pattern was indexed using the tetragonal symmetry, characteristic of the anatase network.

(2) FIG. 2 shows a high-resolution transmission electron micrograph (TEM) obtained from the phase prepared according to example 1.

(3) FIG. 3 shows the Ti2p XPS core spectrum obtained from the phase prepared according to example 1.

(4) FIG. 4 shows a .sup.19F Magic-Angle-Spinning NMR spectrum of the phase prepared according to example 1.

(5) FIG. 5 shows the correlation between the synthesis temperature and the chemical composition of Ti.sub.1-x-y.sub.x+yO.sub.2-4(x+y)F.sub.4x(OH).sub.4y. The Ti (4a) site occupancy was determined by structural analysis of diffraction data.

(6) FIG. 6 shows the potential vs. capacity of a Li/Ti.sub.0.78.sub.0.22F.sub.0.40(OH).sub.0.48O.sub.1.12 cell cycled between 1 and 3V under 20 mA/g. Inset: Voltage profile of a Li/TiO.sub.2 cell.

(7) FIG. 7 shows the quasi-equilibrium voltage obtained by the galvanostatic intermittent titration technique. The Li/Ti.sub.0.78.sub.0.22F.sub.0.40(OH).sub.0.48O.sub.1.12 cell was intermittently discharged at a C-rate of C/10 (315 mA/g) for 20 min followed by 20 hours of relaxation. The x-axis refers to the number of Li ions inserted into Ti.sub.0.78.sub.0.22F.sub.0.40(OH).sub.0.48O.sub.1.12 electrode.

(8) FIG. 8 shows the rate capacity of a Li/Ti.sub.0.78.sub.0.22F.sub.0.40(OH).sub.0.48O.sub.1.12 cell. For comparison purposes, data obtained for a Li/TiO.sub.2 cell under 335 mA/g are also indicated.

DETAILED DESCRIPTION

(9) The present invention relates to methods for the preparation of titanium-based compounds having an anatase type structure with cationic vacancies arising from oxygen to fluorine/hydroxyl groups substitution. The degree of cationic vacancies can be controlled by the amount of fluorine/OH groups substituting oxygen within the anatase network. The general chemical formula of the compound prepared is Ti.sub.1-x-y.sub.x+yF.sub.4x(OH).sub.4yO.sub.2-4(x+y), where represents a cationic vacancy and x and y are such that their sum is between 0.01 and 0.5, or between 0.04 and 0.5, the upper limit being excluded.

(10) The presence of cationic vacancies within the network provides additional vacant sites to host lithium ions and increase the ionic mobility, therefore potentially contributing to a higher energy/power density being achieved.

(11) The invention further relates to electrochemical cells using the titanium-based compounds herein prepared, as electrode with structural arrangement/chemical formula that enables, a lithium storage mechanism contributing to a high power and a high-energy density which can be obtained. The modification of the structural arrangement through control of the chemical composition induces a variation in the electrochemical response when tested as negative electrode in lithium batteries. Indeed, the occurrence of cationic vacancies and fluorine atoms within the network induces a reversible solid solution behavior upon lithium intercalation as opposed to, the reversible first order transition observed for stoichiometric TiO.sub.2 anatase. Additionally, a significant improvement in terms of rate capability, as compared to pure TiO.sub.2, can be achieved with the present material, when used as electrode, being suitable for high power applications.

(12) The present invention discloses the preparation of titanium-based compounds having an anatase type structure with cationic vacancies induced by partial oxygen substitution by fluorine and hydroxyl groups, and their uses in negative electrodes for lithium-ion batteries.

(13) In some embodiments, this application describes a preparation method using, but not limited to, the following steps: a) Preparation of a solution containing a titanium precursor and a fluorinating agent; and b) Precipitation of a titanium-based compound having the general chemical formula Ti.sub.1-x-y.sub.x+yO.sub.2-4(x+y)F.sub.4x(OH).sub.4y, where represents a cationic vacancy and wherein x and y are numbers such that 0.01(x+y)<0.5, or such that 0.04(x+y)<0.5 for instance, 0.1(x+y)<0.3 wherein x cannot be zero.

(14) For example, the titanium precursor of step (a) is selected from titanium C.sub.2-C.sub.10alkoxides and titanium chloride. For instance, the titanium C.sub.2-C.sub.10alkoxide may be selected from titanium ethoxide, propoxide, isopropoxide and/or butoxide. The fluorinating agent is an agent acting as a source of fluoride anion including, without limitation, hydrogen fluoride (HF), ammonium fluoride (NH.sub.4F), and ammonium hydrogen difluoride (NH.sub.4HF.sub.2). The fluorinating agent may be in the form of a solution, for example, an aqueous solution, e.g. a concentrated hydrofluoric acid solution. For example, the solvent used in the solution of step (a) is an organic solvent or a mixture of organic solvent and water. The organic solvent is selected from C.sub.1-C.sub.10alcohols, dialkylketones (e.g. acetone), ethers and esters. Examples of C.sub.1-C.sub.10alcohols include methanol, ethanol, isopropanol, butanol, and octanol.

(15) In one embodiment, a solution containing a titanium alkoxide, an alcohol and a fluoride ion source is used. The molar ratio of fluoride and titanium ranges preferably from 0.1 to 4, preferably the molar ratio is 2.0. Typically, a solution containing titanium alkoxide, the fluoride and the organic solvent is prepared and then transferred in a sealed container, e.g. a Teflon-lined sealed container. The sealed container is then placed in an oven and subjected to a temperature, for example, within the range of from about 50 C. to about 200 C., or from about 90 C. to about 160 C., or the temperature is set to about 90 C. The duration of the thermal treatment ranges preferably from one to 300 hours, preferably about 12 hours. After filtration, the precipitate is then washed and outgassed overnight, at a temperature ranging from 50 to 400 C. preferably at 150 C.

(16) Several fluorinated anatase compounds, having different chemical compositions, were prepared for examples purposes by a preparation method according to the present application. For comparison purposes, a fluorine-free compound was prepared by thermally treating a fluorinated compound at 450 C. for 4 hours under air atmosphere.

EXAMPLES

(17) The following non-limiting examples illustrate the invention. These examples and the invention will also be better understood with reference to the accompanying figures.

Example 1

(18) A fluorinated anatase was obtained by treating a solution containing 13.5 mmol of titanium isopropoxide (4 mL) and 27 mmol of aqueous HF (40%) in 25 mL of isopropanol, in a sealed container at 90 C. for 12 hours. FIG. 1 presents the X-ray powder diffraction pattern (CuK) recorded on the sample obtained according to this example. The corresponding pattern was indexed using the tetragonal structure with the I4.sub.1/amd space group, which is characteristic of the anatase network. The sample is well crystallized and significant x-ray line broadening was observed indicating small coherence domains.

(19) High-resolution transmission electron microscopy (FIG. 2) revealed that the morphology of the solid consists of agglomerates of particles whose size ranges from 5 to 8 nm. Additionally, hkl-dependent x-ray line broadening and HRTEM indicated the formation of faceted crystals, i.e. platelets, in agreement with a recent article (H. G. Yang et al., 2008, Nature, Vol. 453, pages 638-641) that highlights the role of fluorine atoms in stabilizing metastable surfaces. The specific surface area determined from nitrogen adsorption on the sample prepared according to this example was around 180 m.sup.2/g.

(20) The oxidation state of titanium within the sample was determined using x-ray photo-electron spectroscopy. FIG. 3 represents the Ti2p XPS core spectra with the Ti2p.sub.3/2 core located at 458.9 eV, characteristic of tetravalent titanium.

(21) The fluorine atom content in the sample prepared was assessed using solid-state Nuclear Magnetic Resonance of the fluorine nucleus (.sup.19F). The estimation of the F/Ti molar ratio was performed using a reference (NaF) and led to a ratio of 0.5. The chemical composition of the sample was Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12. For information purposes, the three signals observed in the .sup.19F MAS NMR spectra (FIG. 4) were assigned to various coordination modes of fluorine within the anatase network. The peak centered at 85 ppm was assigned to a fluorine coordinated to three titanium ions. The most intense peak located near 0 ppm is characteristic of bridging fluorine and thus was attributed to fluoride ions located near one vacancy. Finally, the broad signal detected at around 90 ppm was assigned to fluoride ions located near two vacancies, i.e. 1-fold coordinated. From the relative intensity, it was concluded that fluoride ions preferentially adopted a 2-fold coordination, i.e. neighboring one vacancy.

(22) Synchrotron diffraction was further used to obtain crystallographic data of the sample. The results were compared to those of a fluorine-free TiO.sub.2 compound and are summarized in Table 1.

(23) TABLE-US-00001 TABLE 1 Structural parameters obtained by analysis of diffraction data. TiO.sub.2 Ti.sub.0.78.sub.0.22O.sub.1.12F.sub.0.4(OH).sub.0.48 a () 3.7695(5) 3.784(1) c () 9.454(2) 9.448(6) V (.sup.3) 134.33(4) 135.28(10) d.sub.TiO/F () 2*1.972(3) 2*1.984(6) 4*1.925(1) 4*1.929(1) Ti (4a) occupancy 1.00(1) 0.74(4)

(24) Both compounds showed close unit cell parameters and inter-atomic distances values. Refining the rate occupancy of the fluorine-free TiO.sub.2 led to a 100% rate occupancy confirming the stoichiometric composition. On the other hand, the fluorinated compound exhibits 78% of Ti (4a) occupancy rate. Thus, the combination of various techniques including thermal and elemental analyses allow to determine the chemical composition of the sample prepared in this example to be Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12.

Example 2

(25) The content of cationic vacancies in Ti.sub.1-x-y.sub.x+yF.sub.4x(OH).sub.4yO.sub.2-4(x+y) can be controlled synthetically. Various cationic concentrations were obtained by tuning the reaction temperature in the conditions of Example 1, Solutions containing 13.5 mmol of titanium isopropoxide (4 mL) and 27 mmol of aqueous HF (40%) in 25 mL of isopropanol, placed in sealed containers, were treated at different temperatures ranging from 90 to 160 C. for 12 hours. The content in cationic vacancies for the prepared samples was determined by diffraction data analysis. The results displayed in FIG. 5 showed a linear variation of the cationic content as a function of the reaction temperature.

Example 3

(26) Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12 prepared according to example 1 was tested in a Li/Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12 cell. The electrochemical cell is composed of a positive electrode, a negative electrode, and a non-aqueous electrolyte. The positive electrode consisted of a mixture of 80 wt % Ti.sub.0.78.sub.0.22F.sub.0.88O.sub.1.12 powder, 10 wt % carbon, and 10 wt % PVDF binder, coated on a copper foil. The negative electrode was metallic lithium and served as reference. An LP30 commercial solution was used as the non-aqueous electrolyte. It contains LiPF.sub.6 dissolved in a mixture of ethylene carbonate (EC) and di-methyl carbonate (DMC) solvents.

(27) FIG. 6 shows the potential versus capacity curves of a Li/Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12 cell under 20 mA/g for the three first cycles. The voltage window was set between 1 to 3V. The first discharge capacity exceeded by far the theoretical capacity, reaching 490 mAh/g. A large irreversible capacity is observed upon charging, with a charge capacity reaching 230 mAh/g. Such a phenomenon is commonly observed for nanosized titanium based materials and is ascribed to lithium reacting with surface species (H.sub.2O, OH groups, etc). The striking point here is the shape of the discharge (reduction) and charge (oxidation) curves exhibiting a continuous evolution of the potential versus capacity, which indicates that the fluorinated anatase Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12 inserts lithium topotactically in a one-phase process, i.e. a solid solution behavior. This is in contrast with TiO.sub.2 anatase that inserts lithium in a two-phase process (first order transition) according to a tetragonal (I4.sub.1/amd) to orthorhombic (Imma) phase transition characterized by the presence of a Li-plateau at 1.78V (inset in FIG. 6).

(28) To confirm that the reaction with lithium proceeds via a solid solution behavior, the quasi-equilibrium voltage (FIG. 7) was obtained by the galvanostatic intermittent titration technique (GITT). The GITT graph shows a smooth curve emphasizing that lithium is inserted in the Ti.sub.0.78.sub.0.22F.sub.0.4(OH).sub.0.48O.sub.1.12 via a solid solution behavior.

(29) FIG. 8 shows the evolution of the capacity as a function of cycle numbers for a Li/Ti.sub.0.78.sub.0.22F.sub.0.88O.sub.1.12 cell. Excellent capacity retention was obtained under high current density. The Li/Ti.sub.0.78.sub.0.22F.sub.0.88O.sub.1.12 cell can indeed sustain a capacity of 135 mAh/g after 50 cycles under 3335 mA/g. This corresponds to discharging 135 mAh/g in 4 minutes, which is equivalent to a 15 C rate. For comparison purposes, the Li/TiO.sub.2 cell cycled under 335 mA/g reached 165 mAh/g after 10 cycles, showing the superior rate capability of the fluorinated anatase over the fluorine-free sample.

(30) Numerous modifications could be made to any one of the above-described embodiments without departing from the scope of the invention as contemplated. References, patents or scientific literature documents mentioned in the present application are incorporated herein by reference in their entirety for all purposes.