Cathode materials for secondary (rechargeable) lithium batteries

• US 6,514,640 B1
• Filed: 12/24/1997
• Issued: 02/04/2003
• Est. Priority Date: 04/23/1996
• Status: Expired due to Term

• Current Assignee: Hydro-Quebec (Province of Québec)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Nanjundaswamy, Kirakodu S., Goodenough, John B., Padhi, Akshaya K., Masquelier, Christian, Armand, Michel
• Primary Examiner(s): CHANEY, CAROL DIANE
• Application Number:
  US08/998,264
• Time in Patent Office: 1,868 Days
• Field of Search: 429/218.1, 429/224, 429/221, 429/231.1, 429/231.2
• US Class Current: 429/231.1
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: G02F 1/155 Electrodes
• 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 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 4/049 Manufacturing of an active layer by chemical means
• 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 4/1397 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 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

The invention relates to materials for use as electrodes in an alkali-ion secondary (rechargeable) battery, particularly a lithium-ion battery. The invention provides transition-metal compounds having the ordered-olivine, a modified olivine, or the rhombohedral NASICON structure and the polyanion (PO₄)³⁻ as at least one constituent for use as electrode material for alkali-ion rechargeable batteries.

Claims

1. A cathode material for a rechargeable electrochemical cell, said cell also comprising an anode and an electrolyte, the cathode material comprising a compound of the ordered or modified olivine structure having the formula:

2. The battery of claim 1, where M comprises a combination of cations of an element selected from the group consisting of Mn, Fe, Co, and Ni.

3. A secondary battery comprising an anode, a cathode and an electrolyte, said cathode comprising a modified olivine compound as set forth in claim 1.

4. The battery of claim 3, wherein the anode comprises a compound selected from the group consisting of a metallic lithium, a lithium alloy, a lithium-carbon intercalation compound, a lithium-transition metal mixed nitride of antifluorite and a lithium-titanium spinel having the formula Li_{1 a z}Ti₂₋

aO₄ where 0≦

a≦

1/3 and 0≦

z≦

1-2a.

5. The battery of claim 4, wherein said cathode further comprises a conductive additive.

6. The battery of claim 5, wherein said conductive additive is carbon.

7. The battery of claim 4, wherein said cathode further comprises an intercalation material with fast diffusion kinetics.

8. The battery of claim 7, wherein said intercalation material is selected from the group consisting of a lamellar dichalcognenide, a vanadium oxide having the formula VO_a where 2.1≦

a≦

2.5, and a NASICON-related material.

9. The battery of claim 8, wherein said NASICON-related material is selected from the group consisting of Li₃Fe₂(PO₄)₃ and Li₃₋

nFe<sub>2−

n</sub>Ti_nPO₄)₃.

10. The battery of claim 4, wherein said cathode further comprises a polymeric binder.

11. The battery of claim 10, wherein said polymeric binder is selected from the group consisting of a homopolymer of tetrafluoroethylene, a copolymer of tetrafluoroethylene, an ethylene-propylene-diene terpolymer, a polyether, a polyester, a methylmethacrylate-based polymer, an acrylonitrile-based polymer, and a vinylidene fluoride-based polymer.

12. The battery of claim 11, wherein said polymeric binder is a polyether.

13. The battery of claim 12, wherein said polyether further comprises a salt comprising Li cations.

14. The battery of claim 13, wherein said polyether is crosslinked.

15. The battery of claim 13, wherein said polymeric binder is swollen by an aprotic solvent.

16. The battery of claim 15, wherein said aprotic solvent is selected from the group consisting of:

ethylene carbonate, propylene carbonate, dimethylcarbonate, diethylcarbonate, methyl-ethylcarbonate, γ

-butyrolactone, a tetraalkylsulfarnide, a dialkylether of an ethylene glycol having a molecular weight≦

2000.

17. The battery of claim 16, wherein said dialkylether comprises a mixture of mono-, di-, tri, tetra-, and higher oligo-ethylene glycols.

18. The battery of claim 16, wherein said aprotic solvent is a dialkylether of an ethylene glycol having a molecular weight≦

2000.

19. The battery of claim 18, wherein said dialkylether comprises a mono-ethylene glycol.

20. The battery of claim 18, wherein said dialkylether comprises a di-ethylene glycol.

21. The battery of claim 18, wherein said dialkylether comprises a tri-ethylene glycol.

22. The battery of claim 18, wherein said dialkylether comprises a tetra-ethylene glycol.

23. The battery of claim 18, wherein said dialkylether comprises an oligo-ethylene glycol higher than a tetra-ethylene glycol.

24. A cathode material according to claim 1, wherein X is P.

25. A cathode material according to claim 24, wherein X is greater than 0.