Rechargeable lithium battery for tolerating discharge to zero volts

• US 7,101,642 B2
• Filed: 09/30/2002
• Issued: 09/05/2006
• Est. Priority Date: 04/26/2000
• Status: Expired due to Term

• Current Assignee: Quallion, LLC (EnerSys)
• Original Assignee: Quallion, LLC (EnerSys)
• Inventors: Tsukamoto, Hisashi, Kishiyama, Clay, Nagata, Mikito, Nakahara, Hiroshi, Piao, Tiehua
• Primary Examiner(s): Ruthkosky, Mark
• Application Number:
  US10/262,490
• Publication Number:
  US 20030025482A1
• Time in Patent Office: 1,436 Days
• Field of Search: 429/245, 429/223, 429/231.3, 429/231.95
• 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 Damage Potential Threshold (DPT). A method for using a battery capable of tolerating discharge to zero volts is also disclosed.

Claims

1. A rechargeable lithium ion battery, comprising:

a positive electrode having a first active material on a substrate, the first active material including LiNi_xCo<sub>1−

x−

y</sub>M_yO₂ wherein M is an element chosen from the group consisting of Mn, Al, Mg, B, Ti, and Li, and wherein 0.5≦

×

≦

1 and 0<

y≦

0.3;

a negative electrode having second active material on a substrate, the second active material including carbon;

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

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

the electrolyte, the positive electrode and the negative electrode being configured such that the ZCP is lower than the FDP 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

the 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 the predetermined temperature.

3. The battery of claim 1, wherein x≧

0.6.

4. The battery of claim 1, wherein x≦

0.8.

5. The battery of claim 1, wherein y≦

0.05.

6. The battery of claim 1, wherein y≧

0.02.

7. The battery of claim 1, wherein said negative electrode substrate is formed of a material selected from the group consisting of titanium and titanium alloy.

8. The battery of claim 1, wherein the negative electrode substrate is formed of stainless steel.

9. The battery of claim 1, wherein the negative electrode active material consists of carbon.

10. The battery of claim 1, wherein the electrolyte consists of a liquid electrolyte.

11. The battery of claim 10, wherein the liquid electrolyte comprises a lithium salt dissolved in EC:

DEC.

12. The battery of claim 11, wherein the lithium salt is LiPF₆.

13. The battery of claim 1, wherein the predetermined temperature is body temperature.

14. The battery of claim 1, wherein the predetermined temperature is about 37°

C.

15. The battery of claim 1, wherein the predetermined temperature is about 25°

C.

16. 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.

17. The battery of claim 1, wherein the ZCP is greater than about 3 V vs. Li/Li⁺.

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

19. The battery of claim 1, further including a case for housing the positive and negative electrodes;

and wherein

the case is configured for implanting in a patient'"'"'s body.

20. The battery of claim 19, wherein the case is hermetically sealed.

21. The battery of claim 1, wherein the element includes Mg.

22. The battery of claim 1, wherein the element includes B.

23. The battery of claim 1, wherein the element includes Ti.

24. The battery of claim 1, wherein the element includes Li.