Title of Invention	METHOD OF PRODUCING CRYSTALLINE LITHIUM/VANADIUM OXIDE POWDER
Abstract	Method of producing crystalline lithium/vanadium oxide powder The present invention relates to a method for manufacturing a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where x is between 0 and 0.2, comprising: formation of an aqueous suspension starting from an NH4VO3 paste and monohydrated Lithia powder, continuous dehydration of this suspension in a hot gas current at a temperature of between 200 and 600°C to form a dry powder of a precursor with a size grading of between 10 and 100 \|imp, calcinations of this precursor at a temperature of between 380 and 580°C to form a crystalline powder of Li1+xV3O8.

Title of Invention

METHOD OF PRODUCING CRYSTALLINE LITHIUM/VANADIUM OXIDE POWDER

Abstract

Method of producing crystalline lithium/vanadium oxide powder The present invention relates to a method for manufacturing a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where x is between 0 and 0.2, comprising: formation of an aqueous suspension starting from an NH4VO3 paste and monohydrated Lithia powder, continuous dehydration of this suspension in a hot gas current at a temperature of between 200 and 600°C to form a dry powder of a precursor with a size grading of between 10 and 100 |imp, calcinations of this precursor at a temperature of between 380 and 580°C to form a crystalline powder of Li1+xV3O8.

Full Text	Technical field This invention relates to a method for manufacturing a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where x is between 0 and 0.2. This product will be used particularly for manufacturing of electrodes for lithium rechargeable batteries. State of the art All existing methods for the synthesis of Li1+xV3O8 composite oxide use the reaction of a vanadium compound on a lithium salt. They differ depending on whether or not they use a solvent. The use of water as a solvent that leads to the formation of a gel is disclosed in patent US5039582 (PISTOIA). This gel is obtained from LiOH and V2O5 after more than 2 4 hours, and is difficult to filter and to dry. Patent US 6177130 (FREY) describes an aqueous solution of lithia and vanadium acid prepared by passing ammonium metavanadate (MVA) on a resin. This solution is dried and its residue redissolved in an organic solvent to generate a product for application of an optical quality thin layer. For example, use of the organic solvent is mentioned in US patent 5549880 (KOKSBANG) and patent application WO 01/22507 (3M), but there are environment and safety problems at the industrial stage. Regardless of the solvent type, known methods are discontinuous and limited by the filtration step. Without a solvent, it is possible to work on a mix of solids. The final compound is obtained by melting the mix as described in US patent 5013620 (Bridgestone) and in the article by A.D. WADSLEY, Acta Cryst. 10 (1957) 261, or a conversion slightly below the melting point as described in US patent 5520903 (CHANG). These methods introduce the problem of transport and grinding of a material in molten or sintered blocks. US patent 613 6476 (Hydro-Quebec and 3M) discloses the mix of dry powders of a lithium compound and a vanadium compound, grinding by jet, and heating below the melting temperature. The method enables good control of the size grading in all manufacturing steps, with the number of steps being fairly limited. However, the solid method has a number of disadvantages compared with the use of a solvent, which enables a more intimate mix of the reagents and therefore a more efficient reaction, and easier implementation. When synthesizing a crystallized material, crystallisation after solvation can take place at a lower temperature than with a solid method, which is more convenient and more economic. Finally, when one of the reagents is obtained in solution, the method with a solvent eliminates a drying step. The purpose of the invention is to provide an almost continuous method for manufacturing a crystalline powder of Li1+xV3O8, that can be easily industrialised with a limited number of steps, in which the size grading can be controlled in each step, starting from ammonium metavanadate (MVA) and lithia reagents. Object of the invention The object of the invention is a method for making a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where X is between 0 and 0.2, comprising: - formation of an aqueous suspension starting from an NH4VO3 paste and monohydrated lithia powder, - continuous dehydration of this suspension in a hot gas current at a temperature of between 200 and 600 °C to form a dry powder of a precursor with a size grading of between 10 and 100 µm, - calcination of this precursor at a temperature of between 380 and 58 0°C to form a crystalline powder of Li1+xV308. Description of the invention The method begins by putting MVA paste and monohydrated lithia powder into an aqueous suspension, with a mass ratio such that the Li/V stoichiometry required to give Li1+xV3O8 is obtained, where x is between 0 and 0,2. The ratio of solids to the total mass is between 40 and 60%. The use of a solvent enables a more intimate mix of reagents and easier implementation than the solid method. Furthermore, in the special case of synthesis of a single-phase crystallized material, the solvent method requires lower crystallization temperatures than the solid method and therefore a lower energy cost. The use of an aqueous solvent has a technical-economic advantage compared with the method described in US patent 613647 6. The inorganic synthesis procedure of MVA imposes that it should be obtained in the wet state before calcination or drying. The drying step is not useful and the MVA (wet, paste or suspension) may be injected into the process directly, regardless of whether the MVA used is ultra-pure or is an intermediate product of V205 in the hydro-metallurgical cycle for the extraction of vanadium in a mining operation. Furthermore, recycling of the ammonia effluent may be economically and environmentally attractive, if combined with hydro-metallurgy of vanadium that consumes this gas. The suspension thus obtained is kept stirred in a neutral atmosphere, for example a nitrogen atmosphere, for between 1/2 and 24 h and between 20 and 90°C, until it is added into a hot gas jet atomiser, for example a R1NAJET atomiser made by the RIERA NADEU S.A. company. The strong turbulent flows of hot gases (250-600°C) from this instrument enable instantaneous dehydration of the solid product and a precursor of the final product is obtained in the form of a dry powder with a size grading of between 10 and 100 jam. The stirred suspension does not have the rheological characteristics of a gel and the dehydration technology used thus bypasses the difficult filtration step used by other methods according to prior art using the "sol-gel" method. The powder obtained is loaded into a belt furnace performing the calcination step at between 380 and 580°C, avoiding re-agglomeration of the product. This step enables formation of the Li1+xV3O8 product crystallised without degrading the size grading that remains between 10 and 100 µm. This product may optionally be micronised and / or mixed with carbon black. The method according to the invention enables less discontinuous operation than other methods using a solvent. The time necessary to create a contact in a suspension is shorter than the time necessary to form a gel. Thus, the difficult step of filtration of a gel is avoided, and on the contrary the suspension is dehydrated by continuously bringing it into a hot gas jet, for example using an instrument in the RINAJET product range (RIERA NADEU S.A.) with a high mass flow. Description of the figures Figure 1 shows the diffraction diagram of the final product in example 1. Figure 2 shows the diffraction diagram of the final product in example 2. Examples Example 1: standard purity LiV308 4872 g of ALDRICH MVA with purity 98.6% (dry weight) and 584 g of ALDRICH LiOH3H2O with purity 99.6% were put into suspension in distilled water, respecting the ratio of 300 ml of solvent per mole of LiV3Os. The approximately 10 litres of suspension thus produced is kept stirred at 50°C for 24 hours under nitrogen. It is added into a small scale model of instruments in the RINOJET commercial range made by the RIERA NADEU S.A. company at 1 1/h at a hot gas inlet temperature of 280°C. The dehydrated powder thus obtained is calcinated in a tray for 10 hours at 40 0°C and the final result is a product identified by X diffraction as being LiV3O8 with V2O5 as an impurity, for which the most intense line is at 20 = 20.27°, as shown by the diagram in Figure 1. This characterisation is made using a Siemens D-5000 dif f ractometer with the Ka line for copper, with 29 varying from 5 to 100° in steps of 0.02° and 2 s per step. The product contains 2.35% of lithium and 52.2% of vanadium by weight, including 2.21% of V+4. Example 2: high purity LiV308 The first step is to use an innovative method to make high purity MVA, using 150 kg of V0C13 extracted from the applicantf s standard production. This material is injected into a stirred reactor, into an NH4OH solution previously prepared from 1 m3 of water and 90 kg of ammonia. The MVA is precipitated by controlling the temperature and the pH, and is washed and filtered on a fabric and is finally discharged in the form of a wet paste with a humidity of between 30 and 50%. Two batches of the above method are used to extract 216 kg of high purity MVA (dry weight) for a wet weight of 336 kg, with the composition shown in table 1: 31 kg of LiOH3H2O produced by the FMC company, dissolved in distilled water and then mixed with 336 kg of wet MVA, are used to obtain 32 0 1 of suspension. Stirring is continued for 2 4 hours at 4 °C and the product is then added into the SI 008 instrument in the RINOJET product range made by RIERA NADEU S.A. at 60 1/h at a gas inlet temperature of 350°C. 12 0 kg of dehydrated powder is recovered from this test, at 80°C. A few tens of kilograms of the extracted material are calcinated for 10 h at 400°C. The size grading of the final product measured by laser size grading on an instrument made by Malvern Instruments, is such that 90% of the powder by volume is smaller than 15.3 pm. The X-diffraction diagram shown in Figure 2 is the diagram for an Lii.2V3O8 crystal with LiVO3 as the impurity, identifiable by its higher intensity peak at 20 = 18.64°. Characterisation is done on a Siemens D-500 dif f ractometer with the Ka line of copper, varying 20 from 10 to 70°C in steps of 0.04° with 15 s per step, The composition of the product obtained is given in table 2: WE CLAIM: 1. Method for manufacturing a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV308, where x is between 0 and 0.2, comprising: formation of an aqueous suspension starting from an NH4VO3 paste and monohydrated lithia powder, continuous dehydration of this suspension in a hot gas current at a temperature of between 200 and 600°C to form a dry powder of a precursor with a size grading of between 10 and 100 jam, calcination of this precursor at a temperature of between 380 and 580°C to form a crystalline powder of Lii+xV308. 2. Method according to claim 1, wherein the suspension is stirred before being injected into the hot gas current. 3. Method according to either of claims 1 and 2, wherein the size grading of the final product is between 10 and 100 jam. 4. Method according to any of claims 1 to 3, wherein the NH4VO3 paste is a high purity paste obtained by making VOCI3 react with NH4OH.

Full Text

Technical field
This invention relates to a method for manufacturing a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where x is between 0 and 0.2. This product will be used particularly for manufacturing of electrodes for lithium rechargeable batteries.
State of the art
All existing methods for the synthesis of Li1+xV3O8 composite oxide use the reaction of a vanadium compound on a lithium salt. They differ depending on whether or not they use a solvent.
The use of water as a solvent that leads to the formation of a gel is disclosed in patent US5039582 (PISTOIA). This gel is obtained from LiOH and V2O5 after more than 2 4 hours, and is difficult to filter and to dry. Patent US 6177130 (FREY) describes an aqueous solution of lithia and vanadium acid prepared by passing ammonium metavanadate (MVA) on a resin. This solution is dried and its residue redissolved in an organic solvent to generate a product for application of an optical quality thin layer. For example, use of the organic solvent is mentioned in US patent 5549880 (KOKSBANG) and patent application WO 01/22507 (3M), but there are

environment and safety problems at the industrial stage. Regardless of the solvent type, known methods are discontinuous and limited by the filtration step.
Without a solvent, it is possible to work on a mix of solids. The final compound is obtained by melting the mix as described in US patent 5013620 (Bridgestone) and in the article by A.D. WADSLEY, Acta Cryst. 10 (1957) 261, or a conversion slightly below the melting point as described in US patent 5520903 (CHANG). These methods introduce the problem of transport and grinding of a material in molten or sintered blocks.
US patent 613 6476 (Hydro-Quebec and 3M) discloses the mix of dry powders of a lithium compound and a vanadium compound, grinding by jet, and heating below the melting temperature. The method enables good control of the size grading in all manufacturing steps, with the number of steps being fairly limited.
However, the solid method has a number of disadvantages compared with the use of a solvent, which enables a more intimate mix of the reagents and therefore a more efficient reaction, and easier implementation. When synthesizing a crystallized material, crystallisation after solvation can take place at a lower temperature than with a solid method, which is more convenient and more economic. Finally, when one of the reagents is obtained in solution, the method with a solvent eliminates a drying step.
The purpose of the invention is to provide an almost continuous method for manufacturing a crystalline powder

of Li1+xV3O8, that can be easily industrialised with a limited number of steps, in which the size grading can be controlled in each step, starting from ammonium metavanadate (MVA) and lithia reagents.
Object of the invention
The object of the invention is a method for making a crystalline powder of a composite lithium and vanadium oxide with formula Li1+xV3O8, where X is between 0 and 0.2, comprising:
- formation of an aqueous suspension starting from an NH4VO3 paste and monohydrated lithia powder,
- continuous dehydration of this suspension in a hot gas current at a temperature of between 200 and 600 °C to form a dry powder of a precursor with a size grading of between 10 and 100 µm,
- calcination of this precursor at a temperature of between 380 and 58 0°C to form a crystalline powder of Li1+xV308.
Description of the invention
The method begins by putting MVA paste and monohydrated lithia powder into an aqueous suspension, with a mass ratio such that the Li/V stoichiometry required to give Li1+xV3O8 is obtained, where x is between 0 and 0,2. The ratio of solids to the total mass is between 40 and 60%.
The use of a solvent enables a more intimate mix of reagents and easier implementation than the solid method.

Furthermore, in the special case of synthesis of a single-phase crystallized material, the solvent method requires lower crystallization temperatures than the solid method and therefore a lower energy cost.
The use of an aqueous solvent has a technical-economic advantage compared with the method described in US patent 613647 6. The inorganic synthesis procedure of MVA imposes that it should be obtained in the wet state before calcination or drying. The drying step is not useful and the MVA (wet, paste or suspension) may be injected into the process directly, regardless of whether the MVA used is ultra-pure or is an intermediate product of V205 in the hydro-metallurgical cycle for the extraction of vanadium in a mining operation. Furthermore, recycling of the ammonia effluent may be economically and environmentally attractive, if combined with hydro-metallurgy of vanadium that consumes this gas.
The suspension thus obtained is kept stirred in a neutral atmosphere, for example a nitrogen atmosphere, for between 1/2 and 24 h and between 20 and 90°C, until it is added into a hot gas jet atomiser, for example a R1NAJET atomiser made by the RIERA NADEU S.A. company. The strong turbulent flows of hot gases (250-600°C) from this instrument enable instantaneous dehydration of the solid product and a precursor of the final product is obtained in the form of a dry powder with a size grading of between 10 and 100 jam.
The stirred suspension does not have the rheological characteristics of a gel and the dehydration technology

used thus bypasses the difficult filtration step used by other methods according to prior art using the "sol-gel" method.
The powder obtained is loaded into a belt furnace performing the calcination step at between 380 and 580°C, avoiding re-agglomeration of the product. This step enables formation of the Li1+xV3O8 product crystallised without degrading the size grading that remains between 10 and 100 µm. This product may optionally be micronised and / or mixed with carbon black.
The method according to the invention enables less discontinuous operation than other methods using a solvent. The time necessary to create a contact in a suspension is shorter than the time necessary to form a gel. Thus, the difficult step of filtration of a gel is avoided, and on the contrary the suspension is dehydrated by continuously bringing it into a hot gas jet, for example using an instrument in the RINAJET product range (RIERA NADEU S.A.) with a high mass flow.
Description of the figures
Figure 1 shows the diffraction diagram of the final product in example 1.
Figure 2 shows the diffraction diagram of the final product in example 2.

Examples
Example 1: standard purity LiV308
4872 g of ALDRICH MVA with purity 98.6% (dry weight) and 584 g of ALDRICH LiOH3H2O with purity 99.6% were put into suspension in distilled water, respecting the ratio of 300 ml of solvent per mole of LiV3Os.
The approximately 10 litres of suspension thus produced is kept stirred at 50°C for 24 hours under nitrogen. It is added into a small scale model of instruments in the RINOJET commercial range made by the RIERA NADEU S.A. company at 1 1/h at a hot gas inlet temperature of 280°C.
The dehydrated powder thus obtained is calcinated in a tray for 10 hours at 40 0°C and the final result is a product identified by X diffraction as being LiV3O8 with V2O5 as an impurity, for which the most intense line is at
20 = 20.27°, as shown by the diagram in Figure 1. This characterisation is made using a Siemens D-5000
dif f ractometer with the Ka line for copper, with 29 varying from 5 to 100° in steps of 0.02° and 2 s per step. The product contains 2.35% of lithium and 52.2% of vanadium by weight, including 2.21% of V+4.
Example 2: high purity LiV308
The first step is to use an innovative method to make high purity MVA, using 150 kg of V0C13 extracted from the applicantf s standard production. This material

is injected into a stirred reactor, into an NH4OH solution previously prepared from 1 m3 of water and 90 kg of ammonia. The MVA is precipitated by controlling the temperature and the pH, and is washed and filtered on a fabric and is finally discharged in the form of a wet paste with a humidity of between 30 and 50%.
Two batches of the above method are used to extract 216 kg of high purity MVA (dry weight) for a wet weight of 336 kg, with the composition shown in table 1:

31 kg of LiOH3H2O produced by the FMC company, dissolved in distilled water and then mixed with 336 kg of wet MVA, are used to obtain 32 0 1 of suspension. Stirring is continued for 2 4 hours at 4 °C and the product is then added into the SI 008 instrument in the RINOJET product range made by RIERA NADEU S.A. at 60 1/h at a gas inlet temperature of 350°C.
12 0 kg of dehydrated powder is recovered from this test, at 80°C. A few tens of kilograms of the extracted material are calcinated for 10 h at 400°C. The size grading of the final product measured by laser size grading on an instrument made by Malvern Instruments, is such that 90% of the powder by volume is smaller than 15.3 pm. The X-diffraction diagram shown in Figure 2 is the diagram for an Lii.2V3O8 crystal with LiVO3 as the

impurity, identifiable by its higher intensity peak at 20 = 18.64°. Characterisation is done on a Siemens D-500 dif f ractometer with the Ka line of copper, varying 20 from 10 to 70°C in steps of 0.04° with 15 s per step, The composition of the product obtained is given in table 2:

WE CLAIM:
1. Method for manufacturing a crystalline powder of a composite lithium and
vanadium oxide with formula Li1+xV308, where x is between 0 and 0.2, comprising:
formation of an aqueous suspension starting from an NH4VO3
paste and monohydrated lithia powder,
continuous dehydration of this suspension in a hot gas current at a
temperature of between 200 and 600°C to form a dry powder of a
precursor with a size grading of between 10 and 100 jam,
calcination of this precursor at a temperature of between 380 and 580°C
to form a crystalline powder of Lii+xV308.
2. Method according to claim 1, wherein the suspension is stirred before being
injected into the hot gas current.
3. Method according to either of claims 1 and 2, wherein the size grading of the final product is between 10 and 100 jam.
4. Method according to any of claims 1 to 3, wherein the NH4VO3 paste is a high purity paste obtained by making VOCI3 react with NH4OH.

Documents:

600-chenp-2005-abstract.pdf

600-chenp-2005-claims.pdf

600-chenp-2005-correspondnece-others.pdf

600-chenp-2005-correspondnece-po.pdf

600-chenp-2005-description(complete).pdf

600-chenp-2005-drawings.pdf

600-chenp-2005-form 1.pdf

600-chenp-2005-form 18.pdf

600-chenp-2005-form 26.pdf

600-chenp-2005-form 3.pdf

600-chenp-2005-form 5.pdf

600-chenp-2005-pct.pdf

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Patent Number

219176

Indian Patent Application Number

600/CHENP/2005

PG Journal Number

27/2008

Publication Date

04-Jul-2008

Grant Date

25-Apr-2008

Date of Filing

11-Apr-2005

Name of Patentee

MSSA

Applicant Address

Inventors:

#	Inventor's Name	Inventor's Address
1	HARABASZ, ARNAUD
2	POINTU, LIONEL
3	FLACHER, PIERRE
4	LE MOUELLIC, CHRISTIAN

PCT International Classification Number

C01G 31/00

PCT International Application Number

PCT/FR03/02685

PCT International Filing date

2003-09-10

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	02/11370	2002-09-13	France