Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection

• US 6,004,698 A
• Filed: 08/21/1997
• Issued: 12/21/1999
• Est. Priority Date: 08/21/1997
• Status: Expired due to Term

• Current Assignee: United States Department of Energy
• Original Assignee: United States Department of Energy
• Inventors: Ross, Philip N., Richardson, Thomas J.
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): WEINER, LAURA S
• Application Number:
  US08/915,612
• Time in Patent Office: 852 Days
• Field of Search: 429/305, 429/306, 429/304, 429/307, 429/310, 429/312, 429/314, 429/315, 429/322, 429/231.95, 252/62.2
• US Class Current: 429/305
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/4235 Safety or regulating additives or arrangements in electrodes, separators or electrolyte H01M10/4242 takes precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A class of organic redox shuttle additives is described, preferably comprising nitrogen-containing aromatics compounds, which can be used in a high temperature (85° C. or higher) electrochemical storage cell comprising a positive electrode, a negative electrode, and a solid polymer electrolyte to provide overcharge protection to the cell. The organic redox additives or shuttles are characterized by a high diffusion coefficient of at least 2.1×10^-8 cm² /second and a high onset potential of 2.5 volts or higher. Examples of such organic redox shuttle additives include an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene, and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1,2-dione.

Claims

1. A solid polymer electrolyte rechargeable electrochemical cell having a positive electrode, a negative electrode, a solid polymer electrolyte comprising a polyether polymer, and an organic redox shuttle additive selected from the group consisting of an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, 2,3,5,6-tetramethylpyrazine, 1,3,5-tricyanobenzene and a dialkali metal salt of 3-4-dihydroxy-3-cyclobutene-1.2-dione, to protect the cell against overcharging.

2. The electrochemical cell of claim 1 wherein the concentration of said organic redox shuttle additive in said cell is sufficient to permit said redox shuttle additive to carry all of the charging current when said cell is being overcharged.

3. The electrochemical cell of claim 1 wherein said organic redox shuttle additive is further characterized by a diffusion coefficient of at least about 2.1×

10^-8 cm².

4. The electrochemical cell of claim 1 wherein said organic redox shuttle additive is further characterized by an onset voltage of at least about 2.5 volts.

5. The electrochemical cell of claim 1 wherein said positive electrode, said negative electrode, said solid polymer electrolyte, and said organic redox shuttle additive which protects said cell against overcharging are each capable of functioning in said cell at an elevated temperature of at least about 85°

C.

6. The electrochemical cell of claim 1 wherein said negative electrode contains lithium.

7. The electrochemical cell of claim 1 wherein said solid polymer electrolyte includes a lithium compound.

8. An electrochemical cell capable of functioning at a temperature of at least about 85°

C. comprising a positive electrode, a negative electrode, a solid polymer electrolyte, and an organic redox shuttle additive selected from the group consisting of an alkali metal salt of 1,2,4-triazole, an alkali metal salt of imidazole, and 1,3,5-tricyanobenzene to protect the cell against overcharging and further characterized by a diffusion coefficient of at least about 1.4×

10^-7 cm² and an onset voltage of at least about 2.5 volts.

9. The electrochemical cell of claim 8 wherein the concentration of said redox shuttle additive in said cell is sufficient to permit said redox shuttle additive to carry all of the charging current when said cell is being overcharged.

10. The electrochemical cell of claim 8 wherein said negative electrode contains lithium.

11. The electrochemical cell of claim 8 wherein said solid polymer electrolyte includes a lithium compound and an organic polymer.

12. An electrochemical cell capable of functioning at a temperature of at least about 85°

C. comprising a lithium-containing negative electrode, a positive electrode, a solid polymer electrolyte comprising a solid polymer and a lithium compound, and an organic redox shuttle additive selected from the group consisting of an alkali metal salt of 1,2,4-triazole and an alkali metal salt of imidazole to protect the cell against overcharging comprising an aromatic compound containing a plurality of nitrogen atoms and further characterized by a diffusion coefficient of at least about 2.1×

10^-7 cm² and an onset voltage of at least about 2.5 volts, said redox shuttle additive present in said cell in a concentration which is sufficient to permit said redox shuttle additive to carry all of the charging current.

13. The electrochemical cell of claim 12 wherein said redox shuttle additive is further characterized by an onset voltage of at least about 3.0 volts.

14. The electrochemical cell of claim 13 wherein said redox shuttle additive comprises an alkali metal salt of 1,2,4-triazole.