Mixed oxide of titanium and niobium comprising a trivalent metal

Patent metadata

Field	Value
Publication number	US-9698417-B2
Application number	US-201414762824-A
Country	US
Kind code	B2
Filing date	Jan 16, 2014
Priority date	Feb 6, 2013
Publication date	Jul 4, 2017
Grant date	Jul 4, 2017

Abstract

A lithium-free mixed titanium and niobium oxide, including at least one trivalent metal M, and having a molar ratio Nb/Ti greater than 2, said oxide being selected from the group including the material of formula (I) and the material of formula (II):

M x Ti 1−2x Nb 2+x O 7±δ   (I) where 0< x ≦0.20; −0.3≦δ≦0.3;

M x Ti 2−2x Nb 10+x O 29±δ   (II) where 0< x ≦0.40; −0.3≦δ≦0.3.

First claim

The invention claimed is:

1. A lithium-free mixed titanium and niobium oxide, comprising at least one trivalent metal M, and having a molar ratio Nb/Ti greater than 2, wherein said oxide is selected from the group consisting of a material of formula (I) and a material of formula (II):
M x Ti 1−2x Nb 2+x O 7±δ   (I) where 0 <x ≦0.20; −0.3≦δ≦0.3;

M x Ti 2−2x Nb 10±x O 29∓δ   (II) where 0 <x ≦0.40; −0.3≦δ≦0.3.

2. The mixed titanium and niobium oxide of claim 1 , wherein the at least one trivalent metal M is selected from the group consisting of iron, gallium, molybdenum, aluminum, boron, and mixtures thereof.

3. The mixed titanium and niobium oxide of claim 1 , wherein the at least one trivalent metal M is iron.

4. An electrode comprising the mixed titanium and niobium oxide of claim 1 .

5. An Li-ion accumulator comprising the electrode of claim 4 .

6. The mixed titanium and niobium oxide of claim 1 , wherein the at least one trivalent metal M is gallium.

7. The mixed titanium and niobium oxide of claim 1 , having a theoretical specific capacity in a range of 368 mAh/g to 396 mAh/g, inclusive.

8. The mixed titanium and niobium oxide of claim 1 , having a chemical formula Ga 0.10 Ti 0.80 Nb 2.10 O 7 .

9. The mixed titanium and niobium oxide of claim 1 , having a chemical formula Fe 0.10 Ti 0.80 Nb 2.10 O 7 .

10. A method of preparing the mixed titanium and niobium oxide of claim 1 , comprising the steps of:
solvothermally treating a solution containing at least: a titanium precursor, a niobium precursor, and a precursor of the at least one trivalent metal to obtain a mixed titanium and niobium oxide;
optionally, mechanically grinding the mixed titanium and niobium oxide obtained at the end of the solvothermal treatment; and,
calcining the mixed titanium and niobium oxide.

11. The method of claim 10 , comprising performing the calcination step at a temperature in a range from 700° C. to 1,200° C.

12. The method of claim 10 , comprising performing the solvothermal treatment step at a temperature in a range from 200° C. to 250° C.

13. The method of claim 10 , comprising performing the solvothermal treatment step for a duration in a range from 2 hours to 10 hours.

14. The method of claim 10 , wherein the titanium precursor is selected from the group consisting of titanium oxysulfate (TiOSO 4 ); titanium isopropoxide (Ti(OCH(CH 3 ) 2 ) 4 ); titanium chloride (TiCl 4 ); and titanium butoxide (Ti(OC 4 H 9 ) 4 ).

15. The method of claim 10 , wherein the niobium precursor is selected from the group consisting of niobium chloride and niobium ethoxide.

16. The method of claim 10 , wherein the precursor of the at least one trivalent metal is selected from the group consisting of FeCl 3 , Fe(NO 3 ) 3 ; Fe 2 (SO 4 ) 3 ; GaCl 3 ; Ga(NO 3 ) 3 ; Ga 2 (SO 4 ) 3 ; MoCl 3 ; AlCl 3 ; Al(NO 3 ) 3 ; Al 2 (SO 4 ) 3 ; and BCl 3 .

17. The method of claim 10 , comprising performing the calcination step for a duration in a range from 30 minutes to 2 hours.

18. The method of claim 10 , comprising cooling the mixed oxide by 5° C. to 20° C. after the calcination step.

Assignees

• Commissariat Energie Atomique

Inventors

• Buannic Lucienne
• Colin Jean-François
• Rey Marlène

Classifications

• C01G49/0018

  Mixed oxides or hydroxides, (C01G49/0009 takes precedence) · CPC title

• H01M4/485 Primary

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• C01P2006/40

  Electric properties · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• C01G33/006

  Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements · CPC title