Lithium ion battery capable of being discharged to zero volts

• US 6,596,439 B1
• Filed: 09/29/2000
• Issued: 07/22/2003
• Est. Priority Date: 04/26/2000
• Status: Expired due to Term

• Current Assignee: Quallion, LLC (EnerSys)
• Original Assignee: Quallion, LLC (EnerSys)
• Inventors: Kishiyama, Clay, Piao, Tiehua, Tsukamoto, Hisashi, Nagata, Mikito, Nakahara, Hiroshi
• Primary Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/675,287
• Time in Patent Office: 1,026 Days
• Field of Search: 429/221, 429/231.95, 429/245, 429/223, 429/231.3
• US Class Current: 429/245
• CPC Class Codes: A61N 1/378 Electrical supply
• 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 10/42 Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells H01M10/60 takes precedence
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• 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 4/133 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 4/505 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 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/662 Alloys collectors of lead alloys H01M4/685
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/4911 including sealing

Abstract

A lithium ion battery particularly configured to be able to discharge to a very low voltage, e.g. zero volts, without causing permanent damage to the battery. More particularly, the battery is configured to define a Zero Volt Crossing Potential (ZCP) which is lower than a Substrate Dissolution Potential (SDP) to thus avoid low voltage substrate damage. The configuration includes a lithium nickel cobalt oxide positive active material combined with negative electrode comprising a titanium or titamum alloy substrate having a carbon active material formed thereon.

Claims

1. A rechargeable battery comprising:

one positive electrode, said positive electrode comprising a metal substrate having one positive active material formed thereon, said positive active material consisting of a lithium oxide comprising cobalt and nickel;

a negative electrode comprising a metal substrate selected from the group consisting of titanium and titanium alloy having a second active material comprising carbon formed thereon;

an electrolyte wherein said negative electrode and said electrolyte form a solid electrolyte interface (SEI) layer, said SEI layer being susceptible of damage when a voltage potential exceeding a Film Dissolution Potential (FDP) is applied thereto, and wherein said FDP is lower than the maximum positive operating potential of the battery;

said positive and negative electrodes defining a Zero Volt Crossing Potential (ZCP) relative to a reference level when the voltage between said electrodes is zero; and

wherein

said positive and negative electrodes are selected and configured to establish ZCP at a lower level than FDP to prevent dissolution of said SEI layer during storage at a predetermined temperature.

2. The battery of claim 1 wherein said negative electrode substrate is susceptible of permanent damage when a potential exceeding a Substrate Dissolution Potential (SDP) is applied thereto;

and wherein

said positive and negative electrodes are selected and configured to establish ZCP at a lower level than SDP in order to prevent dissolution of the negative substrate during storage at said predetermined temperature.

3. The battery of claim 1 wherein said negative electrode active material consists of carbon.

4. The battery of claim 1 wherein said electrolyte consists of a liquid electrolyte.

5. The battery of claim 4 wherein said liquid electrolyte comprises a lithium salt dissolved in EC:

DEC.

6. The battery of claim 5 wherein said lithium salt is LiPF₆.

7. The battery of claim 1 wherein said predetermined temperature is body temperature.

8. The battery of claim 1 wherein said predetermined temperature is about 37°

C.

9. The battery of claim 1 wherein said predetermined temperature is about 25°

C.

10. The battery of claim 1 further comprising a battery management circuit that attempts to stop battery discharge when the battery voltage reaches 2.5 V, wherein the maximum battery voltage is greater than 2.5 V.

11. The battery of claims 1 wherein said ZCP is greater than about 3 V vs. Li/Li+.

12. The battery of claim 1 wherein said positive electrode has a positive discharge curve having a negative slope over most of said positive discharge curve, wherein said negative slope is more negative than the negative slope over most of the discharge curve of LiCoO₂.

13. The battery of claim 1 further including a hermetically sealed case for housing said positive and negative electrodes.

14. The battery of claim 13 wherein said case is configured to be implanted in a patient'"'"'s body.

15. The battery of claim 13 wherein said case has a volume of less than 30 cc.

16. A rechargeable battery comprising:

one positive electrode, said positive electrode comprising a metal substrate having one positive active material formed thereon, said positive active material consisting of a lithium oxide comprising cobalt and nickel;

a negative electrode comprising a substrate selected from the group consisting of titanium and titanium alloy having a second active material comprising carbon formed thereon;

said negative electrode being susceptible of damage when a voltage exceeding a Damage Potential Threshold (DPT) is applied thereto, and wherein said DPT is lower than the maximum positive operating potential of the battery;

said positive and negative electrodes defining a Zero Volt Crossing Potential (ZCP) relative to a reference level when the voltage between said electrodes is zero; and

wherein

said positive and negative electrodes are selected and configured to define a value of ZCP which is less than the value of DPT at a predetermined temperature.

17. The battery of claims 16 wherein the Damage Potential Threshold (DPT) is defined by a Substrate Dissolution Potential, which is the dissolution potential of the negative electrode substrate relative to said reference level.

18. The battery of claim 16 further comprising a solid electrolyte interface (SEI) formed on the negative electrode, and wherein the Damage Potential Threshold (DPT) is defined by a Film Dissolution Potential (FDP), which is the voltage above which the SEI layer begins to dissolve.

19. The battery of claim 16 wherein said predetermined temperature is body temperature.

20. The battery of claim 16 wherein said predetermined temperature is about 37°

C.

21. The battery of claim 16 wherein said predetermined temperature is 25°

C.

22. The battery of claim 16 further comprising a battery management circuit that attempts to stop battery discharge when the battery voltage reaches 2.5 V, wherein the maximum battery voltage is greater than 2.5 V.

23. The battery of claim 16 wherein said ZCP is greater than about 3 V vs. Li/Li+.

24. The battery of claim 16 wherein said positive electrode has a positive discharge curve having a negative slope over most of said positive discharge curve, wherein said negative slope is more negative than the negative slope over most of the discharge curve of LiCoO₂.

25. The battery of claim 16 wherein further including a hermetically sealed case for housing said positive and negative electrodes.

26. The battery of claim 25 wherein said case is configured to be implanted in a patient'"'"'s body.

27. The battery of claim 25 wherein said case has a volume of less than 30 cc.