Overcharge protection systems for rechargeable batteries

• US 6,248,481 B1
• Filed: 01/07/1999
• Issued: 06/19/2001
• Est. Priority Date: 01/14/1997
• Status: Expired due to Term

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., De Jonghe, Lutgard C., Chu, May-Ying
• Primary Examiner(s): Chaney, Carol
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/227,183
• Time in Patent Office: 894 Days
• Field of Search: 429/50, 429/188, 429/314, 429/340
• US Class Current: 429/340
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: H01M 2200/00 Safety devices for primary or secondary batteries
• 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 4/5815 Sulfides
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Disclosed is an electrochemical device having a shuttle-type redox mechanism for overcharge protection in which the redox reaction is “tuned” with a tuning agent to adjust the potential at which the redox reaction occurs. Such device may be characterized as including the following elements: (1) a negative electrode (e.g., lithium); (2) a positive electrode containing one or more intermediate species (e.g., polysulfides) which are oxidized to one more oxidized species during overcharge; and (3) a tuning species (e.g., an organosulfur compound) which adjusts the rate at which the oxidized species are reduced and thereby adjusts the voltage at which overcharge protection is provided. The oxidized species produced during overcharge move to the negative electrode where they are reduced back to said intermediate species as in a normal redox shuttle. However, the oxidized species react more rapidly than the intermediate species at the negative electrode. Thus, the overcharge protection mechanism becomes more active as the oxidized species'"'"' concentration increases—as occurs during more severe overcharge.

Claims

1. A rechargeable electrochemical energy conversion device resisting damage from overcharge, the rechargeable electrochemical energy conversion device comprising:

a positive electrode other than a sulfur electrode;

a negative electrode;

a sulfur-based additive including at least one of elemental sulfur, a sulfide species, and a polysulfide species; and

an electrolyte in which the polysulfide species, if present, are substantially soluble and the sulfide species, if present, is substantially insoluble, whereby during overcharge a polysulfide species is oxidized to an oxidized polysulfide species which is subsequently reduced by a reaction with the substantially insoluble sulfide species.

2. The rechargeable electrochemical energy conversion device of claim 1, wherein the device has a fully charged voltage of at most about 3.0 volts.

3. The rechargeable electrochemical energy conversion device of claim 1, wherein the device is operated at a temperature of at most about 200°

C.

4. The rechargeable electrochemical energy conversion device of claim 1, wherein the electrolyte is a polymeric electrolyte.

5. The rechargeable electrochemical energy conversion device of claim 4, wherein the polymeric electrolyte includes polyethylene oxide.

6. The rechargeable electrochemical energy conversion device of claim 1, wherein the negative electrode is selected from the group consisting of alkali metals, alkali metal alloys, alkaline earth metals, alkaline earth metal alloys, transition metals, transition metal alloys, intercalation materials, and glass matrix electrodes.

7. The rechargeable electrochemical energy conversion device of claim 1, wherein the substantially insoluble sulfide forms a film on the negative electrode.

8. The rechargeable electrochemical energy conversion device of claim 1, wherein the positive electrode is selected from the group consisting of metal oxides, metal sulfides, and organosulfur electrodes.

9. The rechargeable electrochemical energy conversion device of claim 1, wherein the oxidized polysulfide species has the formula M_yS_x, wherein y=1 or 2 and x is greater than or equal to 6.

10. The rechargeable electrochemical energy conversion device of claim 1, further comprising a tuning species which adjusts the rate at which the oxidized polysulfide species is reduced and thereby adjusts the voltage at which overchargeable protection is provided.

11. The rechargeable electrochemical energy conversion device of claim 1, wherein the electrolyte includes one or more solvents selected from the group consisting of organic carbonates, ethers, sulfoxides, sulfones, acetamides, and aromatic compounds.

12. A method of providing protection against overcharge damage, the method comprising:

providing a rechargeable electrochemical energy conversion device including a positive electrode other than a sulfur electrode, a negative electrode, a sulfur-based additive including at least one of elemental sulfur, a sulfide species, and a polysulfide species, and an electrolyte in which the polysulfide species, if present, are substantially soluble and the sulfide species, if present, is substantially insoluble; and

overcharging the rechargeable electrochemical energy conversion device, whereby during overcharge a polysulfide species is oxidized to an oxidized polysulfide species which is subsequently reduced by a reaction with the substantially insoluble sulfide species.

13. The method of claim 12, wherein the rechargeable electrochemical energy conversion device'"'"'s voltage during overcharge does not exceed about 2 volts over the device'"'"'s fully charged voltage.

14. The method of claim 13, wherein the rechargeable electrochemical energy conversion device'"'"'s voltage during overcharge does not exceed about 1 volt over the device'"'"'s fully charged voltage.

15. The method of claim 12, wherein the rechargeable electrochemical energy conversion device is operated at a temperature of at most about 200°

C.

16. The method of claim 12, wherein the electrochemical energy conversion device includes a polymeric electrolyte having polyethylene oxide.

17. The method of claim 12, wherein the positive electrode is selected from the group consisting of metal oxides, metal sulfides, and organosulfur electrodes.

18. A rechargeable electrochemical energy conversion device resisting damage from overcharge, the device comprising:

a negative electrode;

a positive electrode containing one or more intermediate species which are oxidized to one or more oxidized species during overcharge, which oxidized species can move to said negative electrode where they are reduced back to said intermediate species, the oxidized species reacting more rapidly than the intermediate species at the negative electrode; and

a tuning species which adjusts the rate at which the oxidized species are reduced and thereby adjusts the voltage at which overcharge protection is provided.

19. The rechargeable electrochemical energy conversion device of claim 18, wherein the positive electrode includes an organosulfide compound and the negative electrode includes an alkali or alkaline earth metal.

20. The rechargeable electrochemical energy conversion device of claim 18, wherein the positive electrode includes sulfur and the negative electrode includes an alkaline metal or an alkaline earth metal.

21. The rechargeable electrode electrochemical energy conversion device of claim 20, wherein the intermediate and oxidized species are both polysulfides of the formula M_yS_x, where y=1 or 2, x is greater than or = to 2, and wherein the value of x is greater in the oxidized species than in the intermediate species.

22. The electrochemical conversion device of claim 21, wherein x is greater than or equal to 6 for the oxidized species.

23. The rechargeable electrochemical energy conversion device of claim 21, wherein a compound of formula M_yS forms a film on the negative electrode.

24. The rechargeable electrochemical energy conversion device of claim 23, wherein the negative electrode is lithium or a lithium alloy.

25. The rechargeable electrochemical energy chemical conversion device of claim 18, wherein the negative electrode is selected from the group consisting of alkali metals, alkali metal alloys, alkaline earth metals, alkaline earth metal alloys, transition metals, transition metal alloys, intercalation materials, and glass matrix electrodes.

26. The rechargeable electrochemical energy conversion device of claim 18, wherein the device includes a cell selected from the group consisting of lithium/organosulfur cells, lithium/(inorganic sulfur) cells, lithium/(metal oxide) cells, lithium/(metal sulfides) cells, and carbon anode cells.

27. The rechargeable electrochemical energy conversion device of claim 18, wherein the tuning species is an organic sulfur compound of the general formula (R(S)_y)_n, wherein y is a value between 1 and 6, n is a value between about 2 and 1000, and R is one or more different aliphatic or aromatic organic moieties having between 1 and about 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R includes an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

28. The rechargeable electrochemical energy conversion device of claim 18, wherein the tuning species is an alloying element added to a primary metal component of the negative electrode.

29. The rechargeable electrochemical energy conversion device of claim 18, wherein the tuning species is a surface active agent selected from the group consisting of organoborates, boroxines, polyphosphazenes, phosphates, carbonates, nitrates, and organonitrogen compounds.

30. The rechargeable electrochemical energy conversion device of claim 18, further comprising an electrolyte that includes a solvent selected from the group consisting of alkanes, monocyclic aromatics, and polycyclic aromatics, and wherein the intermediate and oxidized species are polysulfides.