PROCESS FOR THE PREPARATION OF CRYSTALLINE LITHIUM-, VANADIUM-AND PHOSPHATE-COMPRISING MATERIALS

• US 20100283012A1
• Filed: 09/18/2008
• Published: 11/11/2010
• Est. Priority Date: 10/01/2007
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Hibst, Hartmut, Bramnik, Kirill, Lampert, Jordan Keith, Roberts, Brian
• Granted Patent: US 8,506,847 B2
• Time in Patent Office: Days
• US Class Current: 252/507
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The present invention relates to a process for the preparation of compounds of general formula (I) Li_a-bM¹_bV_2-cM²_c(PO₄)_x (I) with M¹: Na, K, Rb and/or Cs, M²: Ti, Zr, Nb, Cr, Mn, Fe, Co, Ni, Al, Mg and/or Sc, a: 1.5-4.5, b: 0-0.6, c: 0-1.98 and x: number to equalize the charge of Li and V and M¹ and/or M², if present, wherein a−b is >0, by providing an essentially aqueous mixture comprising at least one lithium-comprising compound, at least one vanadium-comprising compound in which vanadium has the oxidation state +5 and/or +4, and at least one M¹-comprising compound, if present, and/or at least one M²-comprising compound, if present, and at least one reducing agent which is oxidized to at least one compound comprising at least one phosphorous atom in oxidation state +5, drying and calcining.

Claims

1. A process for the preparation of compounds of general formula (I)

Li_a-bM¹_bV_2-cM²_c(PO₄)_x 

 

(I)

wherein M¹, M², a, b, c and x have the following meanings;

M¹;

Na, K, Rb and/or Cs,

M²;

Ti, Zr, Nb, Cr, Mn, Fe, Co, Ni, Al, Mg and/or Sc,

a;

1.5-4.5,

b;

0-0.6,

c;

0-1.98 and

x;

number to equalize the charge of Li and V, and M¹ and/or M², if present,

wherein a−

b is >

0,

comprising

(A) providing an essentially aqueous mixture comprising at least one lithium-containing compound, at least one vanadium-containing compound in which vanadium has the oxidation state +5 and/or +4, and at least one M¹-containing compound, if present, and/or at least one M²-containing compound, if present, and at least one reducing agent which is oxidized to at least one compound comprising at least one phosphorous atom in oxidation state +5,

(B) drying the mixture provided in (A), in order to obtain a solid compound and

(C) calcining the solid compound obtained from (B) at a temperature of 300 to 950°

C.

2. The process according to claim 1, wherein the essentially aqueous solution which is provided in (A) additionally comprises at least one compound comprising at least one phosphorous atom in oxidation state +5.

3. The process according to claim 1, wherein the at least one reducing agent which is oxidized to at least one compound comprising at least one phosphorous atom in oxidation state +5 is chosen from the group consisting of H₃PO₃, (NH₄)H₂PO₃, (NH₄)₂HPO₃, (NH₄)₃PO₃, H₃PO₂, (NH₄)H₂PO₂, (NH₄)₂HPO₂, (NH₄)₃PO₂ and mixtures thereof.

4. The process according to claim 2, wherein the at least one compound comprising at least one phosphorous atom in oxidation state +5 which is added in (A) is chosen from the group consisting of H₃PO₄, (NH₄)H₂PO₄, (NH₄)₂HPO₄, (NH₄)₃PO₄ and mixtures thereof.

5. A compound according to general formula (I)

(I)Li_a-bM¹_bV_2-cM²_c(PO₄)_x 

 

(I)

wherein M¹, M², a, b, c and x have the following meanings;

M¹;

Na, K, Rb and/or Cs,

M²;

Ti, Zr, Nb, Cr, Mn, Fe, Co, Ni, Al, Mg and/or Sc,

a;

1.5-4.5,

b;

0-0.6,

c;

0-1.98 and

x;

number to equalize the charge of Li and V, and M¹ and/or M², if present,

wherein a−

b is >

0,

obtained by a process according to claim 1.

6. A method of using a compound according to claim 5 for the preparation of a cathode of a lithium-ion battery or an electrochemical cell.

7. A cathode for a lithium-ion battery, comprising at least one compound according to claim 5.

8. A process for the preparation of a mixture comprising at least one compound according to general formula (I)

Li_a-bM¹_bV_2-cM²_c(PO₄)_x 

 

(I)

wherein M¹, M², a, b, c and x have the following meanings;

M¹;

Na, K, Rb and/or Cs,

M²;

Ti, Zr, Nb, Cr, Mn, Fe, Co, Ni, Al, Mg and/or Sc,

a;

1.5-4.5,

b;

0-0.6,

c;

0-1.98 and

x;

number to equalize the charge of Li and V, and M¹ and/or M², if present,

wherein a−

b is >

0,

and at least one electrically conducting material comprising

(D) providing an essentially aqueous mixture comprising at least one electrically conducting material, at least one lithium-containing compound, at least one vanadium-containing compound in which vanadium has the oxidation state +5 and/or +4, and at least one M¹-containing compound, if present, and/or at least one M²-containing compound, if present, and at least one reducing agent which is oxidized to at least one compound comprising at least one phosphorous atom in oxidation state +5,

(E) drying the mixture provided in (D), in order to obtain a solid compound and

(F) calcining the solid compound obtained from (E) at a temperature of 300 to 950°

C.

9. The process according to claim 8, wherein the essentially aqueous solution which is provided in (D) additionally comprises at least one compound comprising at least one phosphorous atom in oxidation state +5.

10. The process according to claim 8, wherein the at least one reducing agent which is oxidized to at least one compound comprising at least one phosphorous atom in oxidation state +5 is chosen from the group consisting of H₃PO₃, (NH₄)H₂PO₃, (NH₄)₂HPO₃, (NH₄)₃PO₃, H₃PO₂, (NH₄)H₂PO₂, (NH₄)₂HPO₂, (NH₄)₃PO₂ and mixtures thereof.

11. The process according to claim 8, wherein the electrically conducting material is chosen from the group consisting of carbon black, graphite, carbon fibres, carbon nanofibres, carbon nanotubes, electrically conducting polymers and mixtures thereof.

12. A mixture, comprising at least one compound according to general formula (I)

Li_a-bM¹_bV_2-cM²_c(PO₄)_x 

 

(I)

wherein M¹, M², a, b, c and x have the following meanings;

M¹;

Na, K, Rb and/or Cs,

M²;

Ti, Zr, Nb, Cr, Mn, Fe, Co, Ni, Al, Mg and/or Sc,

a;

1.5-4.5,

b;

0-0.6,

c;

0-1.98 and

x;

number to equalize the charge of Li and V, and M¹ and/or M², if present,

wherein a−

b is >

0,

and at least one electrically conducting material, obtained by a process according to claim 8.

13. A method of using a mixture according to claim 12 for the preparation of a cathode of a lithium ion battery or an electrochemical cell.

14. A cathode for a lithium ion battery, comprising a mixture according claims 12.