Method of making lithium-containing materials

• US 6,528,033 B1
• Filed: 01/18/2000
• Issued: 03/04/2003
• Est. Priority Date: 01/18/2000
• Status: Expired due to Term

• Current Assignee: Lithium Werks Technology BV
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Swoyer, Jeffrey, Barker, Jeremy, Saidi, M. Yazid
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US09/484,919
• Time in Patent Office: 1,141 Days
• Field of Search: 423/306, 423/593, 423/594, 423/599, 423/596, 423/598, 423/179.5, 429/218.1, 429/219, 429/220, 429/221, 429/223, 429/224
• US Class Current: 423/306
• CPC Class Codes: C01B 25/37 Phosphates of heavy metals
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01G 21/00 Compounds of lead
• CPC Class Codes: C01G 31/00 Compounds of vanadium
• CPC Class Codes: C01G 39/00 Compounds of molybdenum
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/0566 Liquid materials
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/582 Halogenides
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y10T 156/1002 : with permanent bending or reshaping or surface deformation of self sustaining lamina
• CPC Class Codes: Y10T 29/10 : Battery-grid making

Abstract

The invention provides novel lithium-mixed metal materials which, upon electrochemical interaction, release lithium ions, and are capable of reversibly cycling lithium ions. The invention provides a rechargeable lithium battery which comprises an electrode formed from the novel lithium-mixed metal materials. Methods for making the novel lithium-mixed metal materials and methods for using such lithium-mixed metal materials in electrochemical cells are also provided. The lithium-mixed metal materials comprise lithium and at least one other metal besides lithium. Preferred materials are lithium-mixed metal phosphates which contain lithium and two other metals besides lithium.

Claims

1. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials comprising a metal compound, a lithium compound, and carbon, where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion;

wherein said lithium compound is selected from the group consisting of lithium carbonate, lithium phosphate, lithium oxide, lithium vanadate, and mixtures thereof.

2. The method of claim 1 wherein said metal compound is a compound of a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Ti, Cr, and mixtures thereof.

3. The method of claim 2 wherein said metal compound is selected from the group consisting of Fe₂O₃, V₂O₅, FePO₄, VO₂, Fe₃O₄, LiVO₃, NH₄VO₃, and mixtures thereof.

4. The method of claim 1 wherein said metal compound is a metal oxide or a metal phosphate.

5. The method of claim 1 wherein said metal compound is V₂O₅, and said lithium compound is lithium carbonate.

6. The method of claim 1 wherein said heating is conducted in a non-oxidizing atmosphere.

7. The method of claim 6 wherein said non-oxidizing atmosphere comprises gas selected from the group consisting of argon;

nitrogen;

a mixture of carbon monoxide and carbon dioxide generated by said heating of said carbon in said starting materials; and

mixtures thereof.

8. The method of claim 6 wherein said non-oxidizing atmosphere is a vacuum.

9. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials comprising a metal oxide;

lithium carbonate;

carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and

a compound containing a phosphate group; and

heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said phosphate group.

10. The method of claim 9 wherein said starting materials consist of:

iron oxide;

a hydroxide selected from the group consisting of magnesium hydroxide and calcium hydroxide;

lithium carbonate;

a phosphate selected from the group consisting of diammonium hydrogen phosphate and ammonium dihydrogen phosphate; and

carbon.

11. The method of claim 9 wherein said starting materials consist of lithium carbonate, iron oxide and a phosphate of a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.

12. The method of claim 9 wherein said heating is conducted in a non-oxidizing atmosphere.

13. The method of claim 12 wherein said non-oxidizing atmosphere comprises gas selected from the group consisting of argon;

nitrogen;

a mixture of carbon monoxide and carbon dioxide generated by said heating of said carbon in said starting materials; and

mixtures thereof.

14. The method of claim 12 wherein said non-oxidizing atmosphere is a vacuum.

15. A method of making a compound which comprises:

mixing starting materials in particle form, said starting materials comprising a metal compound, a lithium compound selected from the group consisting of lithium acetate (LiOOCCH₃), lithium nitrate (LiNO₃), lithium oxalate (Li₂C₂O₄), lithium oxide (Li₂O), lithium phosphate (Li₃PO₄), lithium dihydrogen phosphate (LiH₂PO₄), lithium vanadate (LiVO₃), and lithium carbonate (Li₂CO₂), and carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a single phase reaction product.

16. The method of claim 15 wherein said metal compound is a compound of a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Ti, Cr, and mixtures thereof.

17. The method of claim 15 wherein said starting materials include a second metal compound having a second metal ion which is not reduced and which forms a part of said reaction product.

18. The method of claim 15 wherein said starting materials include a second metal compound which is a compound of a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.

19. The method of claim 18 wherein said second metal compound is selected from the group consisting of magnesium hydroxide and calcium hydroxide.

20. The method of claim 15 wherein said starting materials include a phosphate compound is selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and mixtures thereof.

21. The method of claim 15 wherein said metal compound is a metal oxide or a metal phosphate.

22. The method of claim 15 wherein said metal compound is V₂O₅, and said lithium compound is lithium carbonate.

23. The method of claim 15 wherein said mixing and heating are conducted in a first stage by mixing starting materials consisting of iron oxide, diammonium hydrogen phosphate and carbon and heating said first stage mixed starting materials at a temperature sufficient to produce iron phosphate;

and in a second stage by mixing starting materials consisting of said iron phosphate and lithium phosphate and heating said second stage mixed starting materials at a temperature sufficient to form lithium iron phosphate represented by the nominal formula LiFePO₄.

24. The method of claim 15 wherein said heating is conducted at a ramp rate of up to about 10°

C. per minute to an elevated temperature of between about 400°

C. and about 1200°

, and then maintaining said elevated temperature until said reaction product is formed.

25. The method of claim 24 wherein said elevated temperature is maintained for between several minutes to several hours.

26. The method of claim 15 wherein said heating is conducted in a non-oxidizing atmosphere.

27. The method of claim 26 wherein said non-oxidizing atmosphere comprises gas selected from the group consisting of argon;

nitrogen;

a mixture of carbon monoxide and carbon dioxide generated by said heating of said carbon in said starting materials; and

mixtures thereof.

28. The method of claim 26 wherein said non-oxidizing atmosphere is a vacuum.

29. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials comprising a first metal compound, a lithium compound, a second metal compound, and carbon, where carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of starting materials without full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion, wherein the second metal compound has a second metal ion which is not reduced and which forms a part of said reaction product.

30. The method of claim 29 wherein the second metal compound comprises a compound of a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, and mixtures thereof.

31. The method of claim 30 wherein said second metal compound is selected from the group consisting of magnesium hydroxide and calcium hydroxide.

32. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials comprising a metal compound, a lithium compound, a phosphate compound, and carbon, where said carbon is present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a reaction product comprising lithium and said reduced metal ion, wherein said reaction product is a lithium metal phosphate.

33. The method of claim 32 wherein said phosphate compound is selected from the group consisting of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and mixtures thereof.

34. A two-stage method for making a lithium iron phosphate, wherein:

the first stage comprises mixing starting materials comprising iron oxide, diammonium hydrogen phosphate and carbon, and heating said first stage mixed starting materials at a temperature sufficient to produce iron phosphate; and

the second stage comprises mixing starting materials comprising said iron phosphate and lithium phosphate, and heating said second stage mixed starting materials at a temperature sufficient to form the lithium iron phosphate represented by the nominal formula LiFePO₄.

35. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials consisting of lithium carbonate, iron phosphate, diammonium hydrogen phosphate, a hydroxide selected from the group consisting of magensium hydroxide and calcium hydroxide, and carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials without full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said phosphate group.

36. A method of making a lithium mixed metal compound by reaction of starting materials which comprises:

mixing starting materials in particle form, said starting materials comprising an oxide of a transition metal selected from Groups 4 to 11 inclusive of the Periodic Table having a +2 valence state, a compound of a metal selected from Groups 2, 12, and 14 of the Periodic Table having a +2 valence state, a lithium compound selected from the group consisting of lithium carbonate and lithium dihydrogen phosphate;

a phosphate group containing compound selected from the group diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate, and mixtures thereof; and

carbon present in an amount sufficient to reduce the oxidation state of at least one metal ion of said starting materials wihtout full reduction to an elemental state; and

heating said starting materials at a temperature sufficient to form a single phase reaction product comprising lithium, said reduced metal ion, and said phosphate group.