Overcharge and overdischarge protection of ambient temperature secondary lithium cells

• US 5,278,000 A
• Filed: 09/02/1992
• Issued: 01/11/1994
• Est. Priority Date: 09/02/1992
• Status: Expired due to Fees

• Current Assignee: The United States Government As Represented By The Administrator of The National Aeronautics and SPA
• Original Assignee: United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration
• Inventors: Attia, Alan I., Huang, Chen-kuo, Surampudi, Subbarao, Halpert, Gerald
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US07/942,491
• Time in Patent Office: 496 Days
• Field of Search: 429/191, 429/194, 429/218, 429/223, 429/224, 429/91, 429/61, 429/90
• US Class Current: 429/91
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/42 Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells H01M10/60 takes precedence
• CPC Class Codes: H01M 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 6/5055 End of discharge indicated by a voltage step
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A cathode additive is provided for protecting an ambient temperature secondary lithium cell from over-charging or over-discharging. The cathode additive is chosen to create an upper voltage plateau which is slightly higher than a characteristic charge cutoff voltage of the cathode of the cell. The cathode additive additionally creates a lower voltage plateau which is slightly lower than the characteristic discharge cutoff voltage of the cell. Preferably the cathode additive is a transition metal oxide or a sulfide may, for example, include a mixture of Li₂ Mn₂ O₄ and Li₀.1 MoO₂.

Claims

1. In a secondary lithium cell susceptible to over-charging or overdischarging, the improvement being:

a cathode additive for incorporating into a cathode of the cell, the cathode having a charge cutoff voltage and a discharge cutoff voltage, the cathode additive yielding an upper voltage plateau within the cell upon the application of an overcharge voltage to the cell, said upper voltage plateau being slightly higher than the charge cutoff voltage of the cathode and yielding a lower voltage plateau within the cell upon the application of an overdischarge voltage to the cell, said lower voltage plateau being slightly lower than the discharge cutoff voltage plateau of the cathode.

2. The improvement of claim 1, wherein the additive is a transition metal oxide.

3. The improvement of claim 1, wherein the additive is a sulfide.

4. The improvement of claim 2, wherein the cathode additive is selected from a group consisting of Li_x Mn₂ O₄, Li_x MoO₂, Li_x CoO₂, Li_x NiO₂, and Li_x M_y Mn.sub.(2-y) O₄, wherein M is Co, Cr, or Fe.

5. The improvement of claim 1, wherein the cathode additive is a mixture of Li₂ Mn₂ O₄ and Li₀.1 MoO₂.

6. The improvement of claim 1, wherein the secondary lithium cell is selected from a group consisting of Li--TiS₂, Li--MoS₂, Li--NbSe₃, Li--V₂ O₅, Li--MnO₂, and Li_x C--Li_x CoO₂.

7. The improvement of claim 1, wherein the secondary lithium cell is a liquid electrolyte cell.

8. The improvement of claim 1, wherein the secondary lithium cell is a solid state cell.

9. The improvement of claim 8, wherein the secondary lithium cell is a polymeric electrolyte cell.

10. The improvement of claim 1, wherein the upper and lower plateaus are separated by at least 1000 millivolts.

11. The improvement of claim 1, wherein the additive is an electron and lithium ion conductor.

12. The improvement of claim 1, wherein the additive is a single compound additive which creates a sharp transition between the upper and lower voltage plateaus.

13. The improvement of claim 1, wherein the additive is incorporated into the cathode to a concentration of less than 15% by weight.

14. In a multicell rechargeable lithium battery susceptible to over-charging and overdischarging, the improvement being:

a cathode additive for incorporating into a cathode of each cell of the multicell battery, said cathode additive selected from a group consisting of Li_x Mn₂ O₄, Li_x MoO₂, Li_x CoO₂, Li_x NiO₂, and Li_x M_y Mn.sub.(2-y) O₄, wherein M is Co, Cr, or Fe, said secondary lithium cell being of a type selected from a group consisting of Li--TiS₂, Li--MOS₂, Li--NbSe₃, Li--V₂ O₅, Li--MnO₂, and Li_x C--Li_x CoO₂, each cathode having a charge cutoff voltage and a discharge cutoff voltage, the cathode additive yielding an upper voltage plateau within each respective cell upon the application of an overcharge voltage to the respective cell, said upper voltage plateau being slightly higher than the charge cutoff voltage of the cathode of the respective cell and yielding a lower voltage plateau within each respective cell upon the application of an over-discharge voltage to the respective cell, said lower voltage plateau being slightly lower than the discharge cutoff voltage plateau of the cathode of the respective cell.

15. The improvement of claim 14, wherein the cathode additive is a mixture of Li₂ Mn₂ O₄ and Li₀.1 MoO₂.

16. The improvement of claim 14, wherein the secondary lithium cell is a solid state cell.

17. The improvement of claim 16, wherein the secondary lithium cell is a polymeric electrolyte cell.

18. The improvement of claim 14, wherein the upper and lower plateaus are separated by at least 1000 millivolts.

19. The improvement of claim 14, wherein the additive is an electron and lithium ion conductor.

20. The improvement of claim 14, wherein the additive is a single compound additive which creates a sharp transition between the upper and lower voltage plateaus.

21. The improvement of claim 14, wherein the additive is incorporated into the cathode to a concentration of less than 15% by weight.

22. In a multicell rechargeable solid state lithium battery susceptible to over-charging and overdischarging, the improvement being:

a cathode additive for incorporating into a cathode of each cell of the multicell battery, said cathode additive being a mixture of Li₂ Mn₂ O₄ and Li₀.1 MoO₂, said secondary lithium cell being a Li--TiS₂ cell, each cathode having a charge cutoff voltage of about 2.7 volts and a discharge cutoff voltage of about 1.7 volts, the cathode additive yielding an upper voltage plateau of about 2.9 volts within each respective cell upon the application of an overcharge voltage to the respective cell, and yielding a lower voltage plateau of about 1.6 volts within each respective cell upon the application of an overdischarge voltage to the respective cell.