FR3047001A1 - TITANIUM OXY HYDROXIDE COMPOUND AND MANUFACTURING METHOD THEREOF, ELECTRODE AND CATALYST COMPRISING SAME - Google Patents

Abstract

The invention relates to a hydrated titanium oxyhydroxide compound and an electrode and a catalyst comprising this compound. It also relates to a battery, in particular lithium, comprising this electrode. It also relates to a process for producing this hydrated titanium oxyhydroxide compound. The hydrated titanium oxyhydroxide compound according to the invention has the following formula I: TiOx (OH) y, nH2O Formula I in which: - 1.15 ≤ x 1,5 1.55, - 0.9 ≤y≤ 1, 70, and - 0.1 ≤ n ≤ 1, preferably 0.3 ≤ n ≤ 0.5, most preferably n = 0.41, and has an ordered local structure lepidocrocite over a distance of up to 1 nm included as determined by the analysis of the pair distribution function (PDF) obtained by synchrotron diffraction but having a disordered structure over a distance greater than 1 nm, revealed by X-ray diffraction. The invention is applicable in the field of storage and supply of energy, in particular.

Description

The invention relates to a hydrated titanium oxyhydroxide compound and an electrode and a catalyst comprising this compound. It also relates to a battery, in particular lithium, comprising this electrode. It also relates to a process for producing this hydrated titanium oxyhydroxide compound. At present, lithium batteries are increasingly used in many devices, in particular because of their high storage capacity.

In these batteries titanium oxide (TiO 2) has been proposed as a negative electrode material as an alternative to graphite.

Indeed, titanium oxide is a metal oxide that intercalates lithium ions at a potential of about 1.7-1.8 V vs Li / Li +, in the electrolyte stability zone.

The first attempts to use TiO 2 as anode material were made with microcrystalline titanium oxide of rutile or anatase structure, or TiO 2 (B).

However, these electrodes have moderate capacities with a maximum lithium intercalation of 0.5 Li / Ti for the anatase structure and ΤΊΟ2 (B) and no activity for the rutile structure.

The research then turned to the use of titanium oxide nanomaterials, these nanomaterials having a higher specific surface area than microcrystalline titanium oxides and thus higher lithium intercalation kinetics.

Thus, Xiong et al., In "Self-improving anode for lithium-ion batteries based on amorphous to cubic phase transition in TiO2 nanotubes", American Chemical Society, Journal of Physical Chemistry, C 2012, 116, 3181-3187, then proposed to use amorphous titanium nanotubes.

However, these amorphous titanium nanotubes have the disadvantage of presenting, during the first discharge cycle, an irreversible phase transition. In fact, the amorphous titanium nanotubes are then transformed into nanotubes of crystalline titanium oxide crystallizing in the cubic phase.

Above all, the manufacturing process of these nanotubes is very difficult to transpose industrially and the reproducibility of the manufacture of electrodes having the desired properties is also very difficult to industrialize.

Borghols et al. then proposed in "Lithium storage in amorphous Ti02 nanoparticles", Journal of the Electrochemical Society, 157 (5) A582-A588 (2010), to use nanoparticles, having a size of about 2 to 3 nm, of oxide of amorphous titanium as anode material for lithium batteries.

The authors, however, recognize the presence of about 5% of small crystalline domains mainly having the anatase structure. They also indicate that when the material they describe is used as anode in a lithium battery, the first discharge cycle shows a fraction of 2.4 Li ions per TiCH formula unit but after this first cycle In discharge, 1.9 Li ions per T1O2 unit remain stored in the TiO2 so that in the other charging and discharging cycles only 0.5 Li ions per T1O2 unit are used. This means that this material is not usable industrially.

Indeed, the cathode is the active lithium reservoir. In the case of the material described in this article, the cathode must provide 2.4 active Li ions per unit of formula TiO 2, to compensate for the lithium initially trapped at the anode. Therefore, it would be necessary to increase the weight of the cathode which would decrease the volume capacity of the battery.

In addition, there is a loss of performance between the first discharge cycle and subsequent cycles, as shown in Figure 4 (a) of this document. The aim of the invention is to provide a titanium-based amorphous material which can be used as anode material for lithium or sodium batteries, having not only high electrochemical performances but also stable over a large number of cycles, without loss of drastic capacity between the first discharge cycle and the following, which, moreover, can be used without destabilizing the electrolyte and which is compatible with different electrolytes, in particular aqueous.

In addition, the material of the invention can be synthesized by a simple method and at low temperature, that is to say at a temperature between 20 and 100 ° C. For this purpose, the invention provides a hydrated titanium oxyhydroxide compound characterized in that it has the following formula I:

TiOx (OH) y, nH2O Formula I in which: - 1.15 <x <1.55, - 0.9 <y <1.70, and - 0.1 <η <1, preferably 0.3 < η <0.5 and more preferably n = 0.41, and in that it has an ordered lepidocrocite structure over a distance of up to 1 nm inclusive as determined by the analysis of the pair distribution function (PDF ) obtained by synchrotron diffraction but having a disordered structure at a distance greater than 1 nm revealed by X-ray diffraction (Ray CuKa, 2 tetha: 10-80 ° C at a scanning speed 0.57min).

Preferably, the hydrated titanium oxyhydroxide according to the invention is characterized in that in formula I, - x = 1.35, - y - 1.30, and - n = 0.41. The invention also provides an electrode characterized in that it comprises a hydrated titanium oxyhydroxide according to the invention. The invention also proposes a battery characterized in that it comprises an electrode according to the invention. The invention also provides a photocatalyst characterized in that it comprises a hydrated titanium oxohydroxide according to the invention.

Finally, the invention provides a process for producing a hydrated titanium oxyhydroxide of the following formula I:

TiOx (OH) y, nH2O Formula I in which: -1.15 <x <1.55, - 0.9 <y <1.70, and - 0.1 <n <0.1, preferably 0, 3 <n <0.5, most preferably n = 0.41, which has an ordered lepidocrocite structure over a distance of up to and including 1 nm as determined by the analysis of the pair distribution function (PDF) obtained by synchrotron diffraction, but having a disordered structure at a distance greater than 1 nm revealed by X-ray diffraction, this process comprising the following steps: a) dissolving a C1 to C5 alkoxide of titanium in a C1 alcohol at C5, at a concentration of titanium alkoxide of between 0.11 M inclusive and 1.8 M excluded, with stirring and at a temperature between 10 and 30 ° C, inclusive limits, b) hydrolysis of the solution obtained at step a) by adding water with stirring, at a temperature between 10 and 30 ° C, with a hydrolysis rate H = ΠΗ2θ / ητί between 1.11 inclusive and 7 e xclu, c) precipitation of a compound of the desired formula, comprising water, at a temperature between 10 and 100 ° C inclusive for a period of between 1 hour and 48 hours, preferably a duration of 12 hours d) recovering the precipitate formed in step c), e) washing with a C1-C5 alcohol the precipitate obtained in step d), and f) drying the washed precipitate obtained in step e) at 80 ° C. C. for 10 hours, and g) optionally removal of the physisorbed water by heating at 100 ° C. for 2 hours under a primary vacuum.

By primary vacuum is meant in the present text, a pressure less than 10'3 mbar.

Preferably, in the process according to the invention: in step a) the C 1 to C 5 alkoxides of titanium / C 1 to C 5 alcohol are chosen from the pairs of titanium ethoxide / ethanol, titanium isopropoxide / isopropanol, and titanium butoxide / butanol; in step e) the C 1 -C 5 alcohol is ethanol. The invention will be better understood and other features and advantages thereof will appear more clearly in the light of the description which follows and which is made with reference to the figures in which: - Figure 1 shows the curve obtained by analysis- thermogravimetric (ATD-ATG) of a compound according to the invention of formula I: TiO 1 ^ (OH)] rio'0.41 H 2 O, - Figure 2 shows the X-ray diffraction pattern (CuKa, 2tetha = 10 -80 ° to 0.5 ° / min.) Of a compound according to the invention of formula I: TiO 2 (SiOH), 3o'0.41H 2 O, - Figure 3 shows the curve obtained by refining the data of a Synchrotron analysis obtained by pair distribution function (PDF) of the compound according to the invention of formula I: ## STR1 ## FIG. 4 is a diagrammatic representation of the lamellar lepidocrocite structure in which , for a distance less than or equal to 1 nm, the compound according to the invention of formula I, - FIG. the first three charge / discharge curves of a lithium battery comprising as anode an electrode comprising a compound of the invention of formula I: vinylidene), and as a 1M LiPF6 electrolyte in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), - Figure 6 shows the evolution of the capacity of a lithium battery comprising an anode comprising a compound according to the invention of formula I: ## STR2 ## and a polyvinylidene fluoride binder, and as a 1 M LiPFf electrolyte. in a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC), at a v / v ratio of 1/1, - Figure 7 shows the first three load / discharge curves of a lithium battery comprising an anode made with a compound according to the invention of formula I: ## STR1 ## using as binder sodium alginate in a 1M LiPFfi electrolyte in a solvent which is a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) at a v / v ratio of 1/1; FIG. 8 shows the first three charging / discharging curves of a lithium battery comprising an anode manufactured with a compound according to invention of formula I: TiO1> 35 (OH) i) 3o'0.41H20 using as binder polyvinylidene fluoride in 1M LiC104 electrolyte in a solvent which is a mixture of propylene carbonate (PC) / dimethoxyethane (DME) / tetrahydrofuran (THF), in a proportion v / v / v of 40/15/45, - Figure 9 shows the first three charge / discharge curves of a lithium battery comprising an anode manufactured with a compound according to the invention of formula I: TiO 1, 35 (OH) 3 O 3 O 3 O 3 H 2 O using polyvinylidene fluoride in an electrolyte as binder M LiClC> 4 in a solvent which is a mixture of ethylene carbonate / dimethyl carbonate, at a v / v ratio of 1/1, - Figure 10 shows the evolution of the capacity (power test) of a battery lithium compound comprising an anode, made from a compound according to the invention of formula I: TiOit35 (OH) i> 3o'0541H20 using as binder polyvinylidene fluoride, consisting of 1 M LiPF6 and 1 M LiClC> 4 in a solvent which is a mixture of ethylene carbonate (EC) / dimethyl carbonate (DMC) at a ratio v / v of 1/1, and in a solvent which is a mixture of propylene carbonate (PC) / dimethoxyethane (DME) / tetrahydrofuran (THF) in a proportion v / v / v of 40/15/45), - figure 11 shows the evolution of the apacity (power test) of a lithium battery comprising an anode manufactured with a compound according to the invention of the formula TiOg35 (OH) i (30o, 41H20 using as binder polyvinylidene fluoride), in according to the number of cycles in charge and discharge, in an electrolyte which is a mixture of 1M LiPF6 and 1M L1CIO4, in a solvent consisting of a mixture EC / DMC in a proportion v / v of 1/1), - FIG. 12 shows the diffractograms of compounds according to the invention of formula I: TiOi> 35 (OH) i; 3o'0.41H 2 O depending on their synthesis temperature; FIG. 13 shows the diffractograms of compounds according to the invention of Formula I: TiO 2 [3s (OH) 1) 3oOI41H 2 O as a function of the degree of hydrolysis (denoted h in FIG. 13 and H in the present text) used during their synthesis, and FIG. 14 shows the diffractograms of compounds according to the invention of formula I: TiO1, 35 (OH) ii3o'0.41H20 as a function of the concentration (denoted C) in alkoxide of titanium used during their synthesis.

In the invention, the terms "disordered structure" and "amorphous structure" denote the structure of a material or compound whose diffractogram obtained by X-ray diffraction (RayCuKa) with a scanning between 10 and 80 ° at a speed of 0.5 ° / min does not show any peaks that are distinguishable from the background noise.

For illustration, examples of diffractograms of materials or compounds according to the amorphous invention are shown in FIG. 2, in FIG. 12 (temperature 30 ° C., 50 ° C., 70 ° C. and 90 ° C.), in FIG. hydrolysis h = 1.11, 3.33 and 7) and in Figure 14 (alkoxide concentration = 0.11 M, 0.22 M, 0.45 M and 0.90 M). The analysis of the pair distribution function (PDF) was performed as described in Peter J. Chupas, Xiangyun Qiu, Jonathan C. Hanson, Peter L. Lee, Clare P. Gray, Simon JL Billinge "Rapid Acquisition Pair Distribution Function (RA-PDF) Analysis, "Journal of Applied Crystallography, 2003, 36, 1342-1347.

The compound of the invention is a hydrated titanium oxyhydroxide having the following formula I:

TiOx (OH) y, nH 2 O in which: -1.15 <x <1.55, - 0.9 <y <1.70, and - 0.1 <n <1, preferably 0.3 <n < 0.5, most preferably n = 0.41,

The hydrated titanium oxyhydroxide compound of formula I of the invention has an amorphous structure, that is, it does not exhibit long-range order, i.e. at a distance greater than 1 nm, as determined by X-ray diffraction.

But it has an ordered local structure over a distance of up to 1 nm inclusive as determined by the analysis of the pair distribution function (PDF).

This orderly local structure is that of Lepidocrocite.

In addition, the compound of formula I of the invention remains amorphous over a distance greater than 1 nm throughout the charging and discharging cycles when it is used as the anode of a lithium battery, unlike the compound titanium oxide described by Xiong et al. cited above.

The compound of the invention does not contain lithium. The absence of this very expensive and highly reactive element represents a real advantage in terms of ease and costs of synthesis.

Still due to the lack of lithium, it is also more easily recyclable. In fact, the absence of lithium makes it possible to use low temperature synthesis methods (that is to say at a temperature of between 10 ° C. and 100 ° C.), thus making it possible to achieve significant savings in 'energy.

In addition, the carbon footprint of lithium extraction is avoided.

The recycling of the material does not require the separation of titanium and lithium elements.

The compound of the invention is manufactured by a process which is also another object of the invention.

This process consists of solvatively precipitating the compound of the invention using sol-gel precursors.

This process for producing a hydrated titanium oxyhydroxide according to the invention which has the following formula I:

Wherein: - 1.15 <x <1.55, - 0.9 <y <1.70, and - 0.1 <n <1, preferably 0.3 < n <0.5, most preferably n = 0.41, and which has an ordered lepidocrocite local structure over a distance of up to 1 nm inclusive as determined by the analysis of the pair distribution function (PDF) obtained by synchrotron diffraction but having a disordered long-distance structure, that is to say over a distance greater than 1 nm, revealed by X-ray diffraction (CuKa) with a diffractogram characteristic of an amorphous compound, characterized in that that it includes the following steps; a) dissolving a C1 to Cs alkoxide of titanium in a C1 to C5 alcohol with stirring and at a temperature between 10 and 30 ° C, inclusive, with a concentration of titanium alkoxide of between 0.11 and M inclusive and 1.8 excluded, b) hydrolysis of the solution obtained in step a) by adding water with stirring, at a temperature between 10 and 30 ° C, limits included, and at a rate of hydrolysis H between 1.11 and 7 excluded, c) precipitation of a desired compound of formula I in hydrated form at a temperature between 10 and 100 ° C for a period of between 1 and 48 hours, preferably 12 hours, d) recovery of the precipitate formed in stage c) by filtration or centrifugation, preferably by centrifugation, e) washing with a C 1 -C 5 alcohol of the precipitate obtained in stage d), f) drying of the washed precipitate obtained in step e) at 80 ° C for 10 hours, g) optionally removal of the physiological water sorbated from the compound obtained in step f) by drying at a temperature of between 80 and 150 ° C., preferably 100 ° C.

In the process of the invention, in step a) the concentration of titanium alkoxide in the alcohol is important.

Indeed, as can be seen in FIG. 14 which represents the evolution of the crystallization of the product obtained by the process of the invention as a function of the concentration of titanium alkoxide, in this case titanium isopropoxide, as soon as this the concentration of titanium alkoxide, denoted C in FIG. 14, is greater than or equal to 1.80 M, the product obtained has an early crystallization, that is to say no longer an amorphous product as revealed by diffraction of the X-rays.

In FIG. 14, the top diffractogram represents the reference diffractogram of titanium oxide of anatase structure.

Also, in the process of the invention, the degree of hydrolysis H of step b) is important.

The degree of hydrolysis H, denoted h in FIG. 13, corresponds to the molar ratio H 2 O added / titanium alkoxide.

And as seen in FIG. 13, when this degree of hydrolysis is greater than or equal to 7, the product obtained has a diffractogram with a beginning of appearance of peaks corresponding to the main stripe of the structure of titanium oxide. anatase whose X reference diffraction pattern is shown in the upper part of Figure 13.

The precipitation temperature used in step c) is also important.

Indeed, as can be seen in FIG. 12, which shows the diffractograms of compounds synthesized at different temperatures, when the precipitation temperature of step c) is greater than or equal to 110 ° C., the product obtained is no longer an amorphous product: it presents a diffractogram characteristic of a crystallized product, which in this case has the structure TiCfr anatase. In step c) the precipitate formed is a compound of formula I intended but containing at least 0.3 moles of water more than the desired compound.

Preferably, in step a), the C 1 -C 5 alkoxide pairs of titanium / C 1 -C 5 alcohol are chosen from the pairs of titanium ethoxide / ethanol, titanium isopropoxide / isopropanol, and titanium butoxide / butanol, and step e) the C1 to C5 alcohol is ethanol.

The precise chemical composition of the compound of formula I of the invention was determined by thermo-gravimetric analysis.

The curve obtained by thermo-gravimetric analysis (ATD-ATG) of a compound of formula I according to the invention of the empirical formula TiC 6 O 6 H n is shown in FIG.

This analysis was carried out using a temperature rise of 25 ° C. to 600 ° C. with a temperature rise ramp of 5 C / min. It was carried out under argon.

As can be seen in FIG. 1, this curve presents a first regular mass loss (constant slope) between 20 ° C. and 100 ° C., attributable to the loss of physisorbed water. Then this curve shows a new loss of mass, with a slope slightly different from the previous, between 100 ° C and 200 ° C. This loss of weight is attributable to the loss of water present in the structure (structural water). The last loss of mass is attributed to OH groups.

Thus, the compound of the formula TiO 3 (OH 2, 12) has the chemical and structural formula TiO 3 (OH) 1, 30 -0, -41H 2 O. The structural analysis of this compound was carried out first by diffraction of X-rays.

The X-ray diffraction pattern obtained is shown in FIG. 2. This diagram is characteristic of an amorphous compound. Nevertheless, the use of synchrotron radiation makes it possible to obtain the pair distribution function (PDF) which accounts for the local order of the compound irrespective of its crystalline state.

The data obtained were compared to different models and the best agreement is presented in figure 3.

This agreement shows that the compound according to the invention adopts locally (over a distance less than or equal to 1 nm), the lamellar structure shown in FIG.

This structure is a Lepidocrocite structure.

In this lepidocrocite structure, the Ti4 + cation is surrounded by six O2 'or OH' ligands forming an octahedron These octahedra (Τϊ (Ο, ΟΗ) ό are linked together by the vertices and edges forming a zig-zag layer. These layers are separated from each other by the presence of structural water.

H NMR spectroscopy has also made it possible to characterize the proton environment in this structure.

The compound of the invention exhibits excellent electrochemical properties when used to make an anode of a lithium battery, as shown by the following examples.

First, the loss of capacity between the first discharge cycle and the next charge cycle is less than 40%. This loss of capacity is represented by the capacity ratio at the first charge / capacity at the first discharge.

For comparison, the loss of capacity obtained with an anode consisting of amorphous titanium oxide nanotubes described by Borghols is between 57 and 63%.

In addition, during the preparation of the anode, various binders can be used, and in particular the water-soluble binders, such as sodium alginate, which reduces the environmental impact during the production of the anode. 'electrode.

The compound of the invention is also compatible with many electrolytes comprising different lithium salts and solvents.

Example 1 Synthesis of the Compound of Formula I TiO1; 35 (OH) 130O, 41H2O

The hydrated oxyhydroxy compound TiO 2 O 2 O 10 O 10 H 2 O is prepared by solvothermal precipitation using sol-gel precursors. The protocol comprises dissolving a titanium isopropoxide (13.5 mmol) in its parent alcohol (isopropanol, 25.29 ml) with stirring. Subsequently, a quantity of water (0.81 mL) defined by the degree of hydrolysis H which is the ratio number of moles of ELO / mole number of titanium alkoxide of 3.33, is added to the solution and stirred for homogenization for 5-15 minutes. The mixture is then placed in a Teflon body and placed in a hermetically sealed steel bomb. The precipitation reaction is carried out by treatment at 90 ° C for 12 hours. After cooling, the solid is recovered and washed with ethanol by centrifugation and then dried at 80 ° C overnight, and the recovered solid is degassed under a vacuum at 100 ° C for 2 hours to completely eliminate the physisorbed water to allow structural characterization and electrochemical testing of this compound.

Although in this example the titanium alkoxide used was titanium isopropoxide other titanium alkoxides, such as ethoxide, isopropoxide or titanium butoxide can also be used in their parent alcohol, c. that is, ethanol for titanium ethoxide, isopropanol for titanium isopropoxide, and butanol for titanium butoxide.

Example 2 Test of the Electrochemical Properties of the Compound Obtained in Example 1

An anode was prepared by mixing 80% by weight of the compound of Example 1, 10% by weight of polyvinylidene fluoride (PVDF) and 10% by mass of Super P® carbon marketed by the company TIMCAL dissolved beforehand. in n-methyl-2-pyrrolidone (NMP).

Lithium insertion-deinsertion reactions are written as follows: x.Li + ΤίΟι, 35 (ΟΗ) ,, 30 · 0.41Η2Ο = Li * TiOU5 (OH) i, 3 (r0.41H2O

Based on the redox couple Ti4 + / Ti3 +, the theoretical capacity (or quantity of charge) that can be stored is 265 mAh.g'1 (for x = 1). The anode obtained in this example was placed in a lithium battery comprising a lithium metal electrode, and using as electrolyte 1 M LIPF6 in a mixture by volume of 1/1, ethylene carbonate (EC) and dimethyl carbonate (DMC).

This battery has been operated at a current density of 20 mAh.g -1 and has an average operating potential of 1.55 V against lithium.

The first three charging and discharging curves of this battery are shown in FIG. 5. The shape of these curves indicates a lithium insertion by a solid solution mechanism, ie a continuous evolution of the potential as a function of the capacity. The first discharge capacity is 330 mAh.g'1 and then in charge, it drops to 215 mAh.g -1 indicating that some of the lithium is trapped by the structure or on the surface of the material. stabilizes around 170-180 mAh.g'1 after 50 cycles, as shown in Figure 6, which shows a good reversibility of the system.

Example 3

This example shows that the PVDF binder can be replaced by a binder soluble in water during the manufacture of the electrode.

Thus, an electrode comprising 80% by weight of the compound of Example 1 was manufactured with 10% by weight of sodium alginate and 10% by mass of Super P® type carbon previously dissolved in water.

This electrode was tested in the same way as in Example 2.

Figure 7 shows the load and discharge curves for the first three charging and discharging cycles of this battery.

As can be seen, the compound of the invention is compatible with a water-soluble binder.

Example 4 Electrochemical Test of the Compound Obtained in Example 1

An electrode was made with the compound obtained in Example 1.

This electrode contains 80% by weight of the compound of Example 1, 10% by weight of polyvinylidene fluoride (PVDF) and 10% by mass of Super P® type carbon dissolved beforehand in n-methyl- 2-pyrrolidone (NMP).

This electrode was used as anode in the same battery as in Examples 2 and 3 but with different electrolytes.

The first electrolyte used consisted of 1 M LiPFg in a solvent which is an EC / DMC mixture at a v / v ratio of 1/1.

The charge and discharge curves obtained during the first three cycles with such a battery are shown in FIG.

The second electrolyte used was an electrolyte consisting of 1 M L1CIO4 in a PC / DME / THF mixture (v / v / v, 40/15/45).

The charge and discharge curves obtained during the first three charging and discharging cycles with this battery are shown in FIG.

The third electrolyte used was an electrolyte consisting of 1 M L1CIO4 in a mixture EC / DMC (v / v, 1/1),

The charge and discharge curves obtained during the first three cycles of charging and discharging with this battery are shown in FIG.

As seen from these figures, the compound obtained in Example 1 is compatible with other lithium salts and solvents.

Example 5: Power test of the batteries obtained in Example 4.

Power tests were carried out for the different batteries mentioned in Example 4.

Figure 10 shows the evolution of the capacitance under different current density (power test) as a function of the number of charge and discharge cycles for the batteries using, as 1M LiPF electrolyte, in an EC mixture / DMC (v / v, 1/1) and a 1M Li CIO4 electrolyte in a PC / DME / THF solvent (v / v / v, 40/15/45) and Figure 11 shows the evolution of the capacitance under different current density (power test) depending on the number of cycles in charge and discharge of a battery using an electrolyte consisting of 1 M LFPFδ in a mixture EC / DMC (v / v, 1/1) and using a 1 M LiClC 4 electrolyte in an EC / DMC mixture (v / v, 1/1).

It can be seen from FIGS. 10 and 11 that the best power handling is obtained with the 1M L1CIO4 electrolyte in a PC / DME / THF mixture (v / v / v, 40/15/45).

Although the foregoing examples all disclose the use of the compound of the invention for the manufacture of an anode of a lithium battery, the compound of the invention can also be used in sodium and magnesium batteries.

In addition, although the foregoing examples all use non-aqueous solvents, the compounds of the invention can be used in aqueous electrolyte batteries.

Also, the compound of the invention can be used as a catalyst, in particular as a photo catalyst because of its band gap at 3.4 eV.

Claims (7)

1. Hydrated titanium hydroxylhydroxide characterized in that it has the following formula I: TiOx (OH) y, nH 2 O Formula I in which: -1.15 <x <1.55, - 0.9 <y < 1.70, and - 0.1 <n <1, preferably 0.3 <n <0.5, most preferably n = 0.41, and in that it has an ordered local structure lepidocrocite over a distance up to and including 1 nm as determined by the analysis of the pair distribution function (PDF) obtained by synchrotron diffraction but having a disordered structure over a distance greater than 1 nm, revealed by X-ray diffraction. Titanium oxyhydroxide according to Claim 1, characterized in that in formula I, -x = 1.35, y = 1.30, and n = 0.41, 3. An electrode characterized in that it comprises a titanium oxyhydroxide according to claim 1 or 2. 4. Battery characterized in that it comprises an electrode according to claim 3. 5. Catalyst characterized in that it comprises a titanium oxohydroxide according to claim 1 or 2. 6. Process for producing a hydrated titanium oxyhydroxide according to claim 1 or 2 of formula I below: TiOx (OH) y, nH20 Formula I in which: -1.15 <x <1.55, - 0 , 9 <y <1.70, and -0.1 <η <1, preferably 0.3 <η <0.5, most preferably n = 0.41, and in that it has a local structure ordered lepidocrocite over a distance of up to and including 1 nm as determined by the analysis of the pair distribution function (PDF) obtained by synchrotron diffraction but having a disordered structure over a distance greater than 1 nm revealed by diffraction of the rays X, characterized in that it comprises the following steps: a) dissolving a C1 to C5 alkoxide of titanium in a C1 to C5 alcohol at an alkoxide concentration of between 0.11 M inclusive and 1, 8 M excluded, with stirring at a temperature of between 10 and 30 ° C, limits included, b) hydrolysis of the solution obtained in step a) by aj stirring water at a temperature between 10 ° and 30 ° C. inclusive, with a degree of hydrolysis H = nH2O / titanium naikoxide between 1.11 and excluding 7, c) precipitation of the compound of formula I desired, hydrated, at a temperature between 0 and 100 ° C limits included for a period of between 1 and 48 hours, preferably 12 hours, d) recovery of the precipitate formed in step c), by filtration or centrifugation, preferably centrifugation, e) washing with a C 1 -C 5 alcohol of the precipitate obtained in step d), f) drying the washed precipitate obtained in step e) at 80 ° C for 10 hours, and g) optionally drying under primary vacuum of the compound obtained in step f) at a temperature between 80 and 150 ° C, preferably at a temperature of 100 ° C, to remove the physisorbed water of the compound obtained in step f). 7. Process according to claim 6, characterized in that: in step a) the C 1 to C 5 alkoxides of titanium / C 1 to C 5 alcohol are chosen from the pairs of titanium ethoxide / ethanol and titanium isopropoxide / isopropanol and titanium butoxide / butanol and in step e) the C 1 to C 5 alcohol is ethanol.