Solid secondary lithium cell based on lithiated zirconium, titanium or hafnium oxide cathode material

• US 6,103,419 A
• Filed: 09/06/1996
• Issued: 08/15/2000
• Est. Priority Date: 09/06/1996
• Status: Expired due to Term

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Koksbang, Rene, Barker, Jeremy, Saidi, M. Yazid
• Primary Examiner(s): Kalafut, Stephen
• Assistant Examiner(s): CHANEY, CAROL DIANE
• Application Number:
  US08/708,232
• Time in Patent Office: 1,439 Days
• Field of Search: 429/218, 429/194
• US Class Current: 429/220
• 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 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• 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 4/525 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: Y02E 60/10 Energy storage using batteries

Abstract

Provided by the present invention is a new cathode material comprised of a lithiated zirconium, titanium or hafnium oxide. The oxide is of the formula Li₂ MXO₄, where M is preferably a transition metal such as Ni, Co, Fe, Mn, V, Cu, or Cr, and X is zirconium, titanium or hafnium. The cathode material provides a useful composite cathode when combined with a polymeric binder and carbon.

Claims

1. A composite cathode comprising a lithiated zirconium, titanium or hafnium oxide composition, a polymeric binder, and carbon, with the oxide composition having the formula Li₂ MXO₄, where M is a transition metal, or a mixture of transition metals, and X is zirconium, or hafnium.

2. The composite cathode of claim 1, wherein M is Ni, Co, Fe, Mn, V, Cu or Cr, or a mixture thereof.

3. The composite cathode of claim 1, wherein X is zirconium.

4. The composite cathode of claim 1, wherein M is Ni, V, Co, Fe, Cu or Mn and X is zirconium.

16. The composite cathode of claim 1, wherein X is hafnium.

5. A secondary electrochemical cell which comprises:

a solvent containing electrolyte interposed between an anode composed of anodic material and cathode composed of cathodic material wherein said electrolyte comprises an inorganic ion salt and a solid polymeric matrix and wherein said cathodic material comprises Li₂ MXO₄, where M is a transition metal, or a mixture of transition metals, and X is zirconium, or hafnium.

6. The secondary electrochemical cell according to claim 5, wherein said cell has an operating voltage of at about 4 volts or greater.

7. The secondary electrochemical cell according to claim 5, wherein said anode comprises a carbon material selected from carbon black, coke, graphite, or mixtures thereof.

8. The secondary electrochemical cell according to claim 5, wherein said anode comprises an intercalation carbon anode.

9. The secondary electrochemical cell according to claim 5, wherein M is Ni, Co, Fe, Mn, V, Cu or Cr, or a mixture thereof.

10. The secondary electrochemical cell according to claim 9, wherein X is zirconium.

11. The secondary electrochemical cell according to claim 5, wherein X is zirconium.

17. The secondary electrochemical cell of claim 5, wherein X is hafnium.

12. A secondary electrochemical cell comprising an anode, a cathode, and interposed therebetween a solid electrolyte comprising a solid polymeric matrix, a solvent electrolyte, and an inorganic salt, wherein the cathode comprises Li₂ MXO₄, where M is a transition metal or a mixture of transition metals, and X is zirconium, or hafnium.

13. The secondary electrochemical cell of claim 12, wherein M is Ni, Co, Fe, Mn, V, Cu or Cr, or a mixture thereof.

14. The secondary electrochemical cell of claim 12, wherein X is zirconium.

15. The secondary electrochemical cell of claim 14, wherein M is Ni, V, Co, Fe, Cu or Mn, or a mixture thereof.

18. The secondary electrochemical cell of claim 12, wherein X is hafnium.

19. A composite cathode comprising a lithiated titanium oxide composition, a polymeric binder, and carbon, with the oxide composition having the formula Li₂ MXO₄, where M is Ni, Co, Fe, Cu, Cr, or a mixture thereof, and X is titanium.

20. A secondary electrochemical cell which comprises:

a solvent containing electrolyte interposed between an anode composed of anodic material and a cathode composed of cathodic material wherein said electrolyte comprises an inorganic ion salt and a solid polymeric matrix and wherein said cathodic material comprises Li₂ MXO₄, where M is Ni, Co, Fe, Cu, Cr, or a mixture thereof, and X is titanium.

21. A secondary electrochemical cell comprising an anode, a cathode, and interposed therebetween a solid electrolyte comprising a solid polymeric matrix, a solvent electrolyte, and an inorganic salt, wherein the cathode comprises Li₂ MXO₄, where M is Ni, Co, Fe, Cu, Cr or a mixture thereof, and X is titanium.