Secondary battery

• US 4,728,588 A
• Filed: 06/01/1987
• Issued: 03/01/1988
• Est. Priority Date: 06/01/1987
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Noding, Stephen A., Siegel, Sanford A.
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US07/056,616
• Time in Patent Office: 274 Days
• Field of Search: 429/127, 429/162, 429/199, 429/192, 429/194, 429/212, 429/213, 252/182.1
• US Class Current: 429/127
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

This invention relates to a secondary battery comprised of a polymer film, and first and second collector plates. The polymer film comprises a polymer, a plasticizer for the polymer, an epoxidized vegetable oil, graphite and a salt disassociatingly solubilized by the plasticizer. The salt has the formula MX_a, wherein X is chloride, bromide or iodide, M is a metal ion having a reduction-oxidation potential greater than that of X and a is the oxidation number of M.

Claims

1. A secondary battery which features:

(a) a polymer film comprised of,

(i) a polymer,

(ii) a plasticizer for said polymer,

(iii) an epoxidized vegetable oil,

(iv) a salt disassociatingly solubilized in said plasticizer, said salt having the formula MX_a wherein,

X is chloride, bromide or iodide,

M is a metal ion having a reduction-oxidation potential greater than that of X, and a is the oxidation number of M, and

(v) graphite; and

(b) first and second collector plates, said first collector plate being in electronic contact with one side of said polymer film and said second collector plate being in electronic contact with the other side of said polymer film.

2. The secondary battery of claim 1 wherein said battery is constructed as a laminate with said polymer film being the center lamina and said first and second collector plates being metal films and comprising the outside laminae.

3. The secondary battery of claim 1 wherein X is iodide.

4. The secondary battery of claim 1 wherein M is selected from the group consisting of Zn, alkali metals and alkaline earth metals.

5. The secondary battery of claim 1 wherein MX_a is CaI₂.

6. The secondary battery of claim 1 wherein MX_a is LiI.

7. The secondary battery of claim 1 wherein said plasticizer is an alkyl ether ester of an acid selected from the group consisting of benzoic acid, terephthalic acid, phthalic acid, adipic acid and mixtures thereof.

8. The secondary battery of claim 1 wherein said plasticizer is selected from the group consisting of:

an alkyl ether ester having the formula, ##STR3## wherein R₁ is a phenyl radical or aliphatic hydrocarbon radical of the formula C_n H_m wherein n is an integer of 1 through 8 inclusive and m is equal to 2n+1, R₂ is either hydrogen or a methyl radical, R₃ is a terephthalate or adipate radical, x is 2, 3 or 4, y is 2, 3 or 4; and

an alkylene glycol alkanoic diester of the formula, ##STR4## wherein X is a whole integer greater than or equal to 2 but less than or equal to 5, n is a whole integer greater than or equal to 4 but less than or equal to 12, and m=2n+1.

9. The secondary battery of claim 8 wherein said plasticizer is di(triethylene glycol butyl ether)terephthalate.

10. The secondary battery of claim 9 wherein said plasticizer is present in an amount within the range of from about 5 to about 50 weight percent based upon the total weight of said polymer film.

11. The secondary battery of claim 8 wherein said plasticizer is di(triethylene glycol butyl ether)adipate.

12. The secondary battery of claim 11 wherein said plasticizer is present in an amount within the range of from about 5 to about 50 weight percent based upon the total weight of said polymer film.

13. The secondary battery of claim 5 wherein said plasticizer is di(triethylene glycol butyl ether)terephthalate.

14. The secondary battery of claim 5 wherein said plasticizer is di(triethylene glycol butyl ether)adipate.

15. The secondary battery of claim 6 wherein said plasticizer is di(triethylene glycol butyl ether)terephthalate.

16. The secondary battery of claim 6 wherein said plasticizer is di(triethylene glycol butyl ether)adipate.

17. The secondary battery of claim 1 wherein said graphite is present as a coat on the sides of said polymer film and said coat has a thickness within the range of from about 0.1 microns to about 10.0 microns.

18. The secondary battery of claim 17 wherein said graphite has an average particle size within the range of from about 0.1 microns to about 1.0 microns.

19. The secondary battery of claim 1 wherein said polymer is selected from the group consisting of poly(vinyl chloride), polyurethane, polystyrene, chlorinated polyethylene, poly(vinylidene chloride), poly(ethylene terephthalate), chlorinated butyl rubber and isoprene/styrene/butadiene block polymers.

20. The secondary battery of claim 1 wherein said polymer is poly(vinyl chloride).

21. The secondary battery of claim 1 wherein said polymer is polyurethane.

22. The secondary battery of claim 1 wherein said epoxidized vegetable oil is epoxidized soybean oil.

23. The secondary battery of claim 22 wherein said polymer is poly(vinyl chloride).

24. The secondary battery of claim 23 wherein MX_a is either CaI₂ or LiI.

25. The secondary battery of claim 24 wherein said plasticizer is di(triethylene glycol butyl ether)terephthalate or di(triethylene glycol butyl ether)adipate or mixtures thereof.

26. The secondary battery of claim 25 wherein said graphite has an average particle size within the range of from about 0.1 microns to about 1.0 microns and is present as a coat on the sides of said polymer film and said coat has a thickness within the range of from about 0.1 microns to about 10 microns.

27. The secondary battery of claim 8 wherein said plasticizer is 2-ethylhexanoic tetraethylene glycol, 2-ethylheptanoic tetraethylene glycol, 2-ethylhexanoic triethylene glycol, 2-ethylheptanoic triethylene glycol or mixtures thereof.

28. The secondary battery of claim 27 wherein said plasticizer is present in an amount within the range of from about 30 to about 60 weight percent based upon the total weight of said polymer film.

29. The secondary battery of claim 5 wherein said plasticizer is 2-ethylhexanoic tetraethylene glycol, 2-ethylheptanoic tetraethylene glycol, 2-ethylhexanoic triethylene glycol, 2-ethylheptanoic triethylene glycol or mixtures thereof.

30. The secondary battery of claim 6 wherein said plasticizer is 2-ethylhexanoic tetraethylene glycol, 2-ethylheptanoic tetraethylene glycol, 2-ethylhexanoic triethylene glycol, 2-ethylheptanoic triethylene glycol or mixtures thereof.

31. The secondary battery of claim 24 wherein said plasticizer is 2-ethylhexanoic tetraethylene glycol, 2-ethylheptanoic tetraethylene glycol, 2-ethylhexanoic triethylene glycol, 2-ethylheptanoic triethylene glycol or mixtures thereof.

32. The secondary battery of claim 31 wherein said graphite has an average particle size within the range of from about 0.1 microns to about 1.0 microns and is present as a coat on the sides of said polymer film and has a thickness within the range of from about 0.1 microns to about 10.0 microns.