Lithiated nickel dioxide and secondary cells prepared therefrom

• US 5,264,201 A
• Filed: 07/23/1990
• Issued: 11/23/1993
• Est. Priority Date: 07/23/1990
• Status: Expired due to Term

• Current Assignee: Moli Energy Limited
• Original Assignee: Her Majesty The Queen In Right Of The Province Of British Columbia
• Inventors: Fong, Rosamaria, Dahn, Jeffery R., Von Sacken, Ulrich
• Primary Examiner(s): Breneman, R. Bruce
• Application Number:
  US07/556,754
• Time in Patent Office: 1,219 Days
• Field of Search: 429/209, 429/218, 429/223, 429/224, 423/593, 423/594, 423/595, 423/596, 423/598, 423/599
• US Class Current: 252/519.1
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/80 Compositional purity
• 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 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• 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: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Lithiated nickel dioxide cathode-active materials for electrochemical cellsaving the formula Li_x Ni_2-x-y M_y O₂, with x being between about 0.8 and about 1.0, M being one or more metals selected from cobalt, iron, chromium, titanium, manganese and vanadium, and y being less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, which material is substantially free of lithium hydroxide and lithium carbonate. The materials are prepared by providing a substantially homogeneous dry intermediate mixture of a starting material containing a nickel compound selected from nickel oxide, nickel hydroxide, and mixtures thereof, and optionally including one or more oxides or hydroxides of a transition metal selected from cobalt, iron, chromium, titanium, manganese and vanadium, together with between about a 10 and about a 25% stoichiometric excess of lithium hydroxide. The mixture is heat treated at a temperature above about 600° C. in an atmosphere substantially free of carbon dioxide and having a partial pressure ratio of oxygen to water vapor greater than about 15, after which any lithium hydroxide or lithium carbonate present in the mixture is removed. Thermally stable lithiated nickel dioxide having a BET surface area less than about 3.0 m² /g, and is also disclosed, as well as electrochemical cells prepared from the disclosed lithiated nickel dioxides.

Claims

1. A method of making a lithiated nickel dioxide cathode-active material for an electrochemical cell, having a formula Li_x Ni_2-x-y M_y O₂, wherein x is between about 0.8 and about 1.0, M is one or more metals selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, which material is substantially free of lithium hydroxide and lithium carbonate, said method comprising the steps of:

providing a substantially homogeneous dry intermediate mixture of a starting material comprising a nickel compound selected from the group consisting of nickel oxide, nickel hydroxide and mixtures thereof, and optionally including one or more oxides or hydroxides of a transition metal selected from the group consisting of cobalt, iron, titanium, manganese, chromium and vanadium, together with between about a 10% and about a 25% stoichiometric excess of lithium hydroxide; and

heat treating said mixture at a temperature above about 600°

C. in an atmosphere substantially free of carbon dioxide having a partial pressure ratio of oxygen to water vapor greater than about 15; and

removing from said mixture any lithium hydroxide or lithium carbonate present.

2. A method as claimed in claim 1, wherein said step of providing said intermediate mixture includes the steps of contacting said starting material with a saturated aqueous solution of lithium hydroxide so as to form a slurry and evaporating water from said slurry.

3. A method as claimed in claim 2, wherein said evaporating step is continued at least until an intermediate mixture substantially devoid of free water is provided.

4. A method as claimed in claim 3, wherein said evaporating step comprises the step of spray-drying said slurry.

5. A method as claimed in claim 1, wherein said heat-treating step is conducted for at least one-half hour.

6. A method as claimed in claim 5, wherein said heat-treating step is conducted for at least one hour.

7. A method as claimed in claim 1, wherein said heat-treating step is conducted at a temperature between above about 700°

C.

8. A method as claimed in claim 7, wherein said heat-treating step is conducted at a temperature above about 800°

C.

9. A method as claimed in claim 1, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.3 Torr.

10. A method as claimed in claim 9, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.1 Torr.

11. A method as claimed in claim 10, wherein in said heat-treating step, said partial pressure of said carbon dioxide in said atmosphere is less than about 0.05 Torr.

12. A method as claimed in claim 1, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 15.

13. A method as claimed in claim 12, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 30.

14. A method as claimed in claim 13, wherein in said heat-treating step, said partial pressure ratio of oxygen to water vapor in said atmosphere is greater than about 100.

15. A method as claimed in claim 1, wherein said removing step comprises the steps of extracting said mixture with neutral water and recovering said mixture.

16. A method as claimed in claim 15, wherein said recovering step comprises filtering said water from said mixture.

17. A method as claimed in claim 16, wherein said removing step further comprises the step of drying said mixture after said filtering step.

18. A method as claimed in claim 17, wherein said drying step comprises drying said filtered mixture at 600°

C. in air.

19. A method as claimed in claim 17, wherein said drying step comprises freeze-drying said filtered mixture.

20. A method as claimed in claim 15, wherein said mixture is extracted with one liter of water for every 300 g of said mixture.

21. A cathode-active material made by a process as claimed in claim 1.

22. An electrochemical cell comprising a cathode containing the cathode-active material as claimed in claim 21, a counter-electrode capable of intercalating lithium, and an electrolyte.

23. An electrochemical cell comprising an electrode comprising lithium, an electrolyte, and a cathode containing the cathode-active material as claimed in claim 21.

38. The electrochemical cell of claim 22, or claim 33 or claim 37, wherein said counter-electrode capable of intercalating lithium, comprises graphitic carbon.

39. The electrochemical cell of claim 38, wherein said carbon is poorly graphitic.

40. The electrochemical cell of claim 39, wherein said poorly graphitic carbon comprises coke.

41. The electrochemical cell of claim 40, wherein said coke comprises petroleum coke.

24. A lithiated nickel dioxide cathode-active material for an electrochemical cell, substantially free of lithium hydroxide or lithium carbonate, having a stoichiometric formula Li_x Ni_2-x-y M_y O₂, wherein x is between about 0.80 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt.

25. The lithiated nickel dioxide of claim 24, having the stoichiometric formula Li_x Ni_2-x O₂, wherein x is between about 0.80 and about 1.00.

26. The lithiated nickel dioxide of claim 25, wherein x is between about 0.90 and about 1.00.

27. The lithiated nickel dioxide of claim 24, having a lithium carbonate content less than about 20,000 ppm by weight.

28. The lithiated nickel dioxide of claim 27, having a lithium carbonate content less than about 10,000 ppm.

29. The lithiated nickel dioxide of claim 28, having a lithium carbonate content less than about 5,000 ppm.

30. The lithiated nickel dioxide of claim 24, having a lithium hydroxide content less than about 20,000 ppm by weight.

31. The lithiated nickel dioxide of claim 30, having a lithium hydroxide content less than about 10,000 ppm.

32. The lithiated nickel dioxide of claim 31, having a lithium hydroxide content less than about 5,000 ppm.

33. An electrochemical cell comprising a cathode containing the lithiated nickel dioxide cathode-active material as claimed in claim 24, an electrolyte, and a counter-electrode capable of intercalating lithium.

42. An electrochemical cell comprising an electrode comprising lithium, an electrolyte and a cathode containing a cathode-active material as claimed in claim 24 or claim 34.

34. A lithiated nickel dioxide cathode-active material for an electrochemical cell having a BET surface area of less than about 3.0 m² /g.

35. The lithiated nickel dioxide of claim 34, having a BET surface area of less than about 1.0 m² /g.

36. The lithiated nickel dioxide of claim 35, having a BET surface area of less than about 0.3 m² /g.

37. An electrochemical cell comprising a cathode containing the cathode-active material as claimed in claim 34, an electrolyte, and a counter-electrode capable of intercalating lithium.

43. An electrochemical cell comprising a cathode containing a cathode-active material having a stoichiometric formula Li_x Ni_2-x-y M_y O₂, wherein x is between about 0.8 and about 1.00, M is one or more metals selected from the group consisting of cobalt, iron, chromium, titanium, manganese and vanadium, and y is less than about 0.2, with the proviso that y is less than about 0.5 for cobalt, an electrolyte, and a counter-electrode capable of intercalating lithium, wherein said cathode-active material is substantially free of lithium hydroxide or lithium carbonate.

44. An electrochemical cell comprising a cathode containing a cathode-active material comprising lithiated nickel dioxide having a BET surface area less than about 3.0 m² /g., an electrolyte, and a counterelectrode capable of intercalating lithium.